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Supporting Information

Table of Contents

I. General procedures ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙2

II. General procedures for preparation of starting materials∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙2

i. General procedures for preparation of starting materials 1a~1f, 1h~1i, 1m~1w ∙∙∙∙∙∙∙∙∙∙∙∙2

ii. General procedures for preparation of starting materials 1j~1l and 1x~y∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙2

iii. General procedures for preparation of starting material 1g ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙3

iv. General procedures for preparation of starting materials 1z~1ag∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙3

III. Characterization data of starting materials ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙3

IV. UV-vis absorption spectra of 1a ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙15

V. General procedures for heteroaryl/aryl rearrangement ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙16

i. General procedures for heteroaryl rearrangement ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙16

ii. General procedures for aryl rearrangement ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙16

VI. Characterization data of rearrangement products ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙16

VII. References ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙29

VIII. Copies of the 1H, 19F and 13C NMR spectra ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙30

Electronic Supplementary Material (ESI) for Chemical Science.This journal is © The Royal Society of Chemistry 2020

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I. General procedures

All reagents and solvents were purchased from commercial sources and used without further purification unless otherwise stated. All reactions were monitored by thin-layer chromatography (TLC). All reactions were carried out in argon atmosphere unless otherwise stated. Column chromatography was performed on silica gel (200-300 mesh) and visualized with ultraviolet light. Ethyl acetate and petroleum ether were used as eluents. 1H, 13C and 19F spectra were recorded at room temperature on a Varian Mercury plus 300 or Bruker AV400 or Agilent INOVA 600 MHz with TMS as an internal standard and CDCl3 as solvent. Fourier transform infrared spectra (FT-IR) were recorded on Agilent Technologies Cary 630 instrument or Bruker TENSOR 27 instrument. HRMS analyses were made by Lanzhou University by means of ESI. Melting points were measured on micro melting point apparatus and uncorrected.

II. General procedures for preparation of starting materials

i. General procedures for preparation of starting materials 1a~1f, 1h~1i, 1m~1w

Starting materials 1a~1f, 1h~1i, 1m~1z were synthesized according to the literature procedures[1]. Salicylaldehyde (1.17 g, 9.6 mmol, 1.2 equiv.), 2-bromopyridine (1.26 g, 8.0 mmol, 1.0 equiv.), CuI (76.2 mg, 0.4 mmol, 0.05 equiv.), picolinic acid (98.5 mg, 0.8 mmol, 0.1 equiv.) and K3PO4 (3.4 g, 16 mmol, 2.0 equiv.) in 16 mL dry DMSO were heated at 80 °C for 24 h under argon. The reaction mixture was cooled to room temperature, 16 mL H2O was added and extracted with 3 × 50 mL EtOAc. The combined organic phases were washed with brine, dried over anhydrous

MgSO4 and concentrated under reduced pressure. Purification by column chromatography on silica (PE/EA = 16/1) affords 1a.

ii. General procedures for preparation of starting materials 1j~1l and 1x~y

Starting materials 1j~1l and 1x~y were synthesized according to the literature procedures[2]. Salicylaldehyde (977 mg, 8.0 mmol, 1.0 equiv.), 2-chloro-5-(trifluoromethyl) pyridine (1.45 g, 8.0 mmol, 1.0 equiv.) and K2CO3 (1.11 g, 8.0 mmol, 1.0 equiv.) in 16 mL dry DMF were heated at 150 °C for 5 h under argon. The reaction mixture was cooled to room temperature, 16 mL H2O was added and extracted with 3 × 40 mL EtOAc. The combined organic phases were washed with brine, dried over anhydrous MgSO4 and concentrated under reduced pressure. Purification by column chromatography on silica (PE/EA = 25/1) affords 1j.

3

iii. General procedures for preparation of starting material 1g

Starting material 1g was synthesized according to the literature procedures[1]. 2-Bromobenzaldehyde (1.78 g, 9.6 mmol, 1.2 equiv.), 5-fluoropyridin-2-ol (0.9 g, 8.0 mmol, 1.0 equiv.), CuI (76.2 mg, 0.4 mmol, 0.05 equiv.), picolinic acid (98.5 mg, 0.8 mmol, 0.1 equiv.) and K3PO4 (3.4 g, 16 mmol, 2.0 equiv.) in 16 mL dry DMSO were heated at 80 °C for 24 h under argon. The reaction mixture was cooled to room temperature, 16 mL H2O was added and extracted with 3 × 50 mL EtOAc. The combined organic phases were washed with brine, dried over anhydrous MgSO4 and concentrated under reduced pressure. Purification by column chromatography on silica (PE/EA = 20/1) affords 1g.

iv. General procedures for preparation of starting materials 1z~1ag

Starting materials 1z~1ag were synthesized according to the literature procedures[2]. To a DMA (16 mL) solution containing 2-fluorobenzaldehydes (0.85 mL, 8.0 mmol, 1.0 equiv.) and 4-hydroxybenzonitrile (954 mg, 8.0 mmol, 1.0 equiv.) were added K2CO3 (1.10 g, 8.0 mmol, 1.0 equiv.), and the reaction mixture was stirred for 3

h at 170 °C under argon atmosphere. The reaction mixture was cooled to room

temperature, diluted with H2O (16 mL), extracted with EtOAc (40 mL x 3), and the

organic layer was washed with brine, dried with anhydrous MgSO4 and concentrated under reduced pressure. Purification by column chromatography on silica (PE/EA = 25/1) affords 1z.

III. Characterization data of starting materials

O

O

N

2-(Pyridin-2-yloxy)benzaldehyde (1a) Light yellow solid, 1.37 g, 86%.1H NMR (300 MHz, CDCl3) δ 10.31 (s, 1H), 8.18 (d, J = 3.4 Hz, 1H), 7.98 (dd, J = 7.8, 1.6 Hz, 1H), 7.77 (td, J = 7.9, 2.0 Hz, 1H), 7.69 – 7.60 (m, 1H), 7.34 (t, J = 7.6 Hz, 1H), 7.18 (d, J = 8.3 Hz, 1H), 7.10 – 7.03 (m, 2H).13C NMR (75 MHz, CDCl3) δ 189.3, 163.5, 156.6, 147.9, 140.1, 135.7, 128.8, 128.6, 125.3, 122.6, 119.4, 112.0; 1H and 13C NMR data agreed with the literature [3].

O

O

N

Me

4

2-((3-Methylpyridin-2-yl)oxy)benzaldehyde (1b)Colorless oil, 0.94 g, 55%1H NMR (300 MHz, CDCl3) δ 10.30 (d, J = 0.6 Hz, 1H), 8.01 – 7.93 (m, 2H), 7.66 – 7.55 (m, 2H), 7.31 (t, J = 7.3 Hz, 1H), 7.16 (d, J = 8.2 Hz, 1H), 7.01 – 6.93 (m, 1H), 2.41 (s, 3H).13C NMR (75 MHz, CDCl3) δ 189.4, 161.8, 156.9, 144.9, 140.4, 135.6, 128.7, 128.4, 125.0, 122.6, 121.9, 119.5, 16.1.IR (KBr, ν / cm-1): 2999, 2855, 2753, 1692, 1650, 1602, 1578, 1479, 1449, 1415, 1274, 1237, 1188, 1114, 1095, 990, 892, 833, 792, 750.HRMS (ESI): calcd. for C13H12NO2 ([M+H]+ ): 214.0863, found: 214.0863.

O

O

N

Me

2-((4-Methylpyridin-2-yl)oxy)benzaldehyde (1c)Colorless oil, 1.16 g, 68%.1H NMR (300 MHz, CDCl3) δ 10.31 (d, J = 0.5 Hz, 1H), 8.00 (dd, J = 20.1, 6.2 Hz, 2H), 7.62 (t, J = 7.2 Hz, 1H), 7.31 (t, J = 7.5 Hz, 1H), 7.15 (d, J = 8.3 Hz, 1H), 6.88 (d, J = 6.6 Hz, 2H), 2.39 (s, 3H).13C NMR (75 MHz, CDCl3) δ 189.4, 163.8, 156.8, 151.8, 147.4, 135.7, 128.7, 128.5, 125.1, 122.5, 120.8, 112.2, 21.2.IR (KBr, ν / cm-1): 3008, 2856, 2757, 1693, 1603, 1562, 1478, 1455, 1394, 1288, 1273, 1215, 1149, 1096, 947, 840, 792, 752, 631.HRMS (ESI): calcd. for C13H12NO2 ([M+H]+ ): 214.0863, found: 214.0862.

O

O

NMe

2-((5-Methylpyridin-2-yl)oxy)benzaldehyde (1d)Colorless oil, 1.28 g, 75%.1H NMR (300 MHz, CDCl3) δ 10.34 (s, 1H), 7.98 (ddd, J = 9.5, 4.8, 1.2 Hz, 2H), 7.67 – 7.54 (m, 2H), 7.37 – 7.25 (m, 1H), 7.13 (d, J = 8.3 Hz, 1H), 6.96 (d, J = 8.3 Hz, 1H), 2.30 (s, 3H).13C NMR (75 MHz, CDCl3) δ 189.5, 161.65, 157.2, 147.6, 140.9, 135.7, 128.9, 128.7, 128.5, 125.0, 122.1, 111.6, 17.7.IR (KBr, ν / cm-1): 2996, 2864, 2757, 1692, 1602, 1580, 1473, 1455, 1377, 1274, 1240, 1154, 1096, 890, 832, 787, 749.HRMS (ESI): calcd. for C13H12NO2 ([M+H]+ ): 214.0863, found: 214.0869.

5

O

O

NOMe

2-((5-Methoxypyridin-2-yl)oxy)benzaldehyde (1e)Colorless oil, 1.47 g, 80%.1H NMR (300 MHz, CDCl3) δ 10.38 (s, 1H), 7.95 (d, J = 7.6 Hz, 1H), 7.85 (d, J = 2.6 Hz, 1H), 7.59 (t, J = 7.7 Hz, 1H), 7.41 – 7.23 (m, 2H), 7.04 (dd, J = 19.7, 8.5 Hz, 2H), 3.84 (s, 3H).13C NMR (75 MHz, CDCl3) δ 189.2, 157.4, 156.8, 152.6, 135.4, 132.6, 128.3, 127.8, 126.3, 124.3, 121.0, 112.5, 55.9.IR (KBr, ν / cm-1): 3002, 2865, 2757, 1698, 1600, 1577, 1488, 1451, 1402, 1318, 1273, 1225, 1173, 1090, 955, 821, 792, 755.HRMS (ESI): calcd. for C13H12NO3 ([M+H]+ ): 230.0812, found: 230.0814.

O

O

N

OMe

2-((6-Methoxypyridin-2-yl)oxy)benzaldehyde (1f)Colorless oil, 0.95 g, 52%.1H NMR (300 MHz, CDCl3) δ 10.34 (d, J = 0.7 Hz, 1H), 7.96 (dd, J = 7.8, 1.8 Hz, 1H), 7.64 – 7.59 (m, 2H), 7.31 (t, J = 7.5 Hz, 1H), 7.19 (dd, J = 8.2, 0.6 Hz, 1H), 6.51 – 6.48 (m, 2H), 3.69 (s, 3H).13C NMR (75 MHz, CDCl3) δ 189.5, 163.4, 162.0, 156.8, 142.0, 135.5, 128.8, 128.3, 125.1, 122.5, 105.2, 102.2, 53.7.IR (KBr, ν / cm-1): 2987, 2858, 2757, 1694, 1604, 1574, 1473, 1428, 1318, 1275, 1231, 1187, 1143, 1097, 1035, 974, 850, 789, 732.HRMS (ESI): calcd. for C13H12NO3 ([M+H]+ ): 230.0812, found: 230.0813.

O

O

NF

2-((5-Fluoropyridin-2-yl)oxy)benzaldehyde (1g)Light yellow oil, 1.23 g, 71%.1H NMR (300 MHz, CDCl3) δ 10.30 (s, 1H), 8.01 – 7.93 (m, 2H), 7.70 – 7.59 (m, 1H), 7.52 (ddd, J = 9.0, 7.3, 3.1 Hz, 1H), 7.34 (t, J = 7.5 Hz, 1H), 7.14 (d, J = 8.3 Hz, 1H), 7.07 (dd, J = 9.0, 3.5 Hz, 1H).13C NMR (75 MHz, CDCl3) δ 189.2, 155.8 (d, J = 119.6 Hz), 146.4, 135.8, 134.8 (d, J = 26.6 Hz), 132.8, 129.1, 128.5, 127.7 (d, J = 21.2 Hz), 125.5, 122.4, 112.9 (d, J = 4.8

6

Hz).19F NMR (376 MHz, CDCl3) δ -134.8 (s).IR (KBr, ν / cm-1): 3016, 2861, 1692, 1602, 1471, 1456, 1385, 1225, 1155, 1096, 1060, 895, 838, 812, 793, 752.HRMS (ESI): calcd. for C12H9FNO2 ([M+H]+ ): 218.0612, found: 218.0615.

O

O

NCl

2-((5-Chloropyridin-2-yl)oxy)benzaldehyde (1h)Colorless oil, 1.16 g, 62%.1H NMR (300 MHz, CDCl3) δ 10.26 (d, J = 0.5 Hz, 1H), 8.09 (dd, J = 2.6, 0.5 Hz, 1H), 7.97 (dd, J = 7.8, 1.5 Hz, 1H), 7.76 – 7.69 (m, 1H), 7.65 (td, J = 8.2, 1.8 Hz, 1H), 7.36 (t, J = 7.4 Hz, 1H), 7.17 (dd, J = 8.2, 0.4 Hz, 1H), 7.04 (dd, J = 8.7, 0.5 Hz, 1H).13C NMR (75 MHz, CDCl3) δ 188.1, 160.9, 155.0, 145.2, 138.9, 134.8, 128.3, 127.6, 125.8, 124.7, 121.7, 111.9.IR (KBr, ν / cm-1): 3034, 2860, 1692, 1603, 1558, 1454, 1396, 1371, 1241, 1209, 1155, 1110, 1062, 889, 829, 805, 766.HRMS (ESI): calcd. for C12H9ClNO2 ([M+H]+ ): 234.0316, found: 234.0318.

O

O

NBr

2-((5-bromopyridin-2-yl)oxy)benzaldehyde (1i)Light yellow oil, 1.11 g, 50%.1H NMR (300 MHz, CDCl3) δ 10.25 (s, 1H), 8.18 (d, J = 2.5 Hz, 1H), 7.96 (dd, J = 7.8, 1.6 Hz, 1H), 7.86 – 7.82 (m, 1H), 7.64 (ddd, J = 8.1, 7.5, 1.8 Hz, 1H), 7.35 (t, J = 7.6 Hz, 1H), 7.16 (dd, J = 8.2, 0.5 Hz, 1H), 6.99 (dd, J = 8.7, 0.5 Hz, 1H).13C NMR (75 MHz, CDCl3) δ 189.0, 162.4, 155.9, 148.5, 142.6, 135.7, 129.3, 128.7, 125.7, 122.7, 114.6, 113.5.IR (KBr, ν / cm-1): 3078, 2858, 1692, 1603, 1574, 1452, 1396, 1364, 1272, 1239, 1211, 1186, 1155, 1089, 1003, 888, 827, 804, 763, 638.HRMS (ESI): calcd. for C12H9BrNO2 ([M+H]+ ): 277.9811, found: 277.9811.

O

O

NCF3

2-((4-(Trifluoromethyl)pyridin-2-yl)oxy)benzaldehyde (1j)Colorless oil, 0.98 g, 46%.

7

1H NMR (300 MHz, CDCl3) δ 10.20 (s, 1H), 8.40 (dd, J = 1.6, 0.9 Hz, 1H), 7.99 (dt, J = 4.7, 2.1 Hz, 2H), 7.73 – 7.65 (m, 1H), 7.42 (t, J = 7.6 Hz, 1H), 7.24 – 7.16 (m, 2H).13C NMR (151 MHz, CDCl3) δ 188.8, 165.7, 155.1, 145.6 (d, J = 4.3 Hz), 136.6 (d, J = 235.1 Hz), 129.8, 128.8, 126.3, 124.4 (d, J = 37.3 Hz), 123.2, 122.8, 122.4 (d, J = 33.8 Hz), 111.8.19F NMR (376 MHz, CDCl3) δ -61.7 (s).IR (KBr, ν / cm-1): 2996, 2865, 1696, 1606, 1478, 1456, 1393, 1328, 1281, 1254, 1210, 1162, 1126, 1077, 1013, 893, 837, 807, 780, 758.HRMS (ESI): calcd. for C13H9F3NO2 ([M+H]+ ): 268.0580, found: 268.0580.

O

O S

N

2-(Benzo[d]thiazol-2-yloxy)benzaldehyde (1k)Orange solid, 1.67 g, 82%.1H NMR (300 MHz, CDCl3) δ 10.37 (d, J = 0.7 Hz, 1H), 8.01 (dd, J = 7.7, 1.8 Hz, 1H), 7.73 – 7.68 (m, 3H), 7.51 – 7.37 (m, 3H), 7.31 (td, J = 7.7, 1.3 Hz, 1H).13C NMR (75 MHz, CDCl3) δ 188.0, 171.2, 156.1, 148.5, 135.8, 132.3, 129.2, 127.6, 126.6, 126.4, 124.5, 121.9 (d, J = 2.3 Hz), 121.4; 1H and 13C NMR data agreed with literature[4].

O

ON

N

Me

Me

2-((3,6-Dimethylpyrazin-2-yl)oxy)benzaldehyde (1l)Yellow solid, M.p. 66 – 67 ℃, 1.32 g, 72%. 1H NMR (300 MHz, CDCl3) δ 10.25 (d, J = 0.7 Hz, 1H), 8.07 (s, 1H), 7.97 (dd, J = 7.8, 1.8 Hz, 1H), 7.63 (ddd, J = 8.3, 7.4, 1.8 Hz, 1H), 7.43 – 7.30 (m, 1H), 7.16 (dd, J = 8.3, 1.0 Hz, 1H), 2.64 (s, 3H), 2.30 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 189.1, 157.3, 155.9, 148.7, 141.4, 138.0, 135.5, 129.2, 128.5, 125.4, 122.6, 20.7, 19.0.IR (KBr, ν / cm-1): 2935, 2858, 1694, 1603, 1540, 1457, 1361, 1281, 1214, 1189, 1158, 1095, 1023, 1006, 883, 851, 810, 759.HRMS (ESI): calcd. for C13H13N2O2 ([M+H]+ ): 229.0972, found: 229.0970.

O

O

N

Me

8

4-Methyl-2-(pyridin-2-yloxy)benzaldehyde (1m)Light yellow oil, 1.52 g, 89%.1H NMR (300 MHz, CDCl3) δ 10.23 (d, J = 0.6 Hz, 1H), 8.18 (dd, J = 5.3, 2.0 Hz, 1H), 7.87 (d, J = 7.9 Hz, 1H), 7.75 (ddd, J = 8.1, 4.9, 2.0 Hz, 1H), 7.13 (dd, J = 8.0, 0.7 Hz, 1H), 7.08 – 7.02 (m, 2H), 6.97 (d, J = 0.4 Hz, 1H), 2.41 (s, 3H).13C NMR (75 MHz, CDCl3) δ 189.0, 163.6, 156.5, 147.8, 147.3, 140.0, 128.7, 126.4, 126.2, 122.9, 119.2, 111.9, 22.1.IR (KBr, ν / cm-1): 3011, 2856, 1689, 1612, 1571, 1496, 1467, 1429, 1239, 1144, 1106, 991, 949, 883, 846, 818, 805, 779, 736, 712.HRMS (ESI): calcd. for C13H12NO2 ([M+H]+ ): 214.0863, found: 214.0870.

O

O

N

Me

3-Methyl-2-(pyridin-2-yloxy)benzaldehyde (1n)White solid, M.p. 67 – 68 ℃, 1.23 g, 72%.1H NMR (300 MHz, CDCl3) δ 10.15 (d, J = 0.7 Hz, 1H), 8.09 (ddd, J = 5.0, 2.0, 0.8 Hz, 1H), 7.82 (ddd, J = 7.7, 1.7, 0.5 Hz, 1H), 7.74 (ddd, J = 8.3, 7.2, 2.0 Hz, 1H), 7.54 (ddd, J = 7.5, 1.7, 0.8 Hz, 1H), 7.30 (t, J = 7.7 Hz, 1H), 7.05 – 6.97 (m, 2H), 2.17 (s, 3H).13C NMR (75 MHz, CDCl3) δ 190.0, 163.8, 154.4, 147.9, 140.1, 137.6, 132.9, 129.6, 126.7, 126.0, 118.8, 110.7, 16.4.IR (KBr, ν / cm-1): 3063, 2861, 1698, 1684, 1587, 1464, 1428, 1392, 1241, 1186, 1142, 1084, 922, 880, 817, 777, 736.HRMS (ESI): calcd. for C13H12NO2 ([M+H]+ ): 214.0863, found: 214.0862.

O

O

N

OMe

3-Methoxy-2-(pyridin-2-yloxy)benzaldehyde (1o)White solid, M.p. 101 – 102 ℃, 1.15 g, 63%.1H NMR (300 MHz, CDCl3) δ 10.24 (d, J = 0.6 Hz, 1H), 8.09 (dd, J = 5.0, 2.0 Hz, 1H), 7.73 (ddd, J = 8.3, 7.2, 2.0 Hz, 1H), 7.56 (dd, J = 7.7, 1.6 Hz, 1H), 7.33 (t, J = 7.9 Hz, 1H), 7.24 (dd, J = 8.1, 1.6 Hz, 1H), 7.07 (d, J = 8.3 Hz, 1H), 7.00 (ddd, J = 7.2, 5.0, 0.8 Hz, 1H), 3.77 (s, 3H).13C NMR (75 MHz, CDCl3) δ 189.7, 163.8, 152.5, 147.6, 145.5, 139.8, 130.3, 126.2,

9

119.6, 118.8, 118.2, 110.7, 56.4.IR (KBr, ν / cm-1): 2995, 2867, 1687, 1673, 1596, 1568, 1467, 1427, 1400, 1317, 1181, 1143, 1063, 991, 911, 878, 817, 779, 740.HRMS (ESI): calcd. for C13H12NO3 ([M+H]+ ): 230.0812, found: 230.0818.

O

O

NBr

5-bromo-2-(pyridin-2-yloxy)benzaldehyde (1p)White solid, M.p. 54 – 55 ℃, 1.49 g, 67%.1H NMR (300 MHz, CDCl3) δ 10.21 (s, 1H), 8.15 (dd, J = 5.4, 2.0 Hz, 1H), 8.06 (d, J = 2.6 Hz, 1H), 7.80 – 7.75 (m, 1H), 7.71 (dd, J = 8.7, 2.6 Hz, 1H), 7.11 – 7.06 (m, 3H).13C NMR (75 MHz, CDCl3) δ 187.9, 163.2, 155.5, 147.8, 140.2, 138.2, 131.4, 130.0, 124.7, 119.7, 118.6, 112.0.IR (KBr, ν / cm-1): 2996, 2856, 1689, 1590, 1572, 1464, 1428, 1388, 1240, 1178, 1143, 1110, 1058, 992, 893, 864, 837, 774.HRMS (ESI): calcd. for C12H9BrNO2 ([M+H]+ ): 277.9811, found: 277.9812.

O

O

NF

5-Fluoro-2-(pyridin-2-yloxy)benzaldehyde (1q)White solid, M.p. 59 – 60 ℃, 0.88 g, 51%.1H NMR (300 MHz, CDCl3) δ 10.21 (d, J = 3.0 Hz, 1H), 8.16 – 8.13 (m, 1H), 7.77 (ddd, J = 8.3, 7.3, 2.0 Hz, 1H), 7.63 (dd, J = 8.2, 3.2 Hz, 1H), 7.34 (ddd, J = 8.9, 7.5, 3.2 Hz, 1H), 7.19 (dd, J = 9.0, 4.3 Hz, 1H), 7.09 – 7.04 (m, 2H).13C NMR (75 MHz, CDCl3) δ 188.2, 163.5, 159.7 (d, J = 246.3 Hz), 152.4 (d, J = 2.5 Hz), 147.7, 140.2, 129.9 (d, J = 6.5 Hz), 124.8 (d, J = 7.7 Hz), 122.7 (d, J = 24.1 Hz), 119.5, 114.3 (d, J = 23.8 Hz), 111.7.19F NMR (376 MHz, CDCl3) δ -116.1 (s).IR (KBr, ν / cm-1): 3068, 2865, 1692, 1594, 1594, 1487, 1466, 1428, 1396, 1245, 1183, 1141, 1099, 1057, 992, 965, 877, 838, 776, 734, 710.HRMS (ESI): calcd. for C12H9FNO2 ([M+H]+ ): 218.0612, found: 218.0613.

O

O

NCl

5-Chloro-2-(pyridin-2-yloxy)benzaldehyde (1r)Light yellow solid, M.p. 52 – 53 ℃, 1.06 g, 57%.

10

1H NMR (300 MHz, CDCl3) δ 10.23 (d, J = 0.6 Hz, 1H), 8.20 – 8.09 (m, 1H), 7.91 (d, J = 2.7 Hz, 1H), 7.81 – 7.73 (m, 1H), 7.57 (ddd, J = 8.7, 2.7, 0.6 Hz, 1H), 7.16 (d, J = 8.7 Hz, 1H), 7.11 – 7.04 (m, 2H).13C NMR (75 MHz, CDCl3) δ 187.9, 163.2, 154.9, 147.8, 140.2, 135.3, 131.1, 129.7, 128.3, 124.4, 119.7, 112.0.IR (KBr, ν / cm-1): 2995, 2866, 1691, 1594, 1464, 1429, 1389, 1242, 1179, 1111, 1058, 992, 870, 839, 774, 736.HRMS (ESI): calcd. for C12H9ClNO2 ([M+H]+ ): 234.0316, found: 234.0319.

O

O

N

Me

OMe

2-((5-Methoxypyridin-2-yl)oxy)-3-methylbenzaldehyde (1s)Colorless oil, 1.65 g, 85%.1H NMR (300 MHz, CDCl3) δ 10.17 (d, J = 0.7 Hz, 1H), 7.81 (dd, J = 7.7, 1.7 Hz, 1H), 7.73 (d, J = 3.1 Hz, 1H), 7.53 (ddd, J = 7.5, 1.7, 0.8 Hz, 1H), 7.36 – 7.23 (m, 2H), 6.96 (dd, J = 8.9, 0.5 Hz, 1H), 3.80 (s, 3H), 2.16 (s, 3H).13C NMR (75 MHz, CDCl3) δ 190.0, 158.1, 154.8, 152.3, 137.5, 132.9, 132.3, 129.7, 127.2, 126.5, 125.8, 110.8, 56.3, 16.3.IR (KBr, ν / cm-1): 2938, 2839, 1681, 1586, 1484, 1465, 1440, 1384, 1233, 1185, 1084, 1031, 1010, 922, 886, 831, 786, 769, 736, 716.HRMS (ESI): calcd. for C14H14NO3 ([M+H]+ ): 244.0968, found: 244.0974.

O

O

N

Me

Me

3-Methyl-2-((5-methylpyridin-2-yl)oxy)benzaldehyde (1t)

Colorless oil, 1.40 g, 77%.1H NMR (300 MHz, CDCl3) δ 10.15 (s, 1H), 7.89 (d, J = 0.9 Hz, 1H), 7.81 (d, J = 7.8 Hz, 1H), 7.53 (d, J = 8.3 Hz, 2H), 7.31 – 7.26 (m, 1H), 6.92 (d, J = 8.4 Hz, 1H), 2.26 (s, 3H), 2.16 (s, 3H).13C NMR (75 MHz, CDCl3) δ 190.0, 162.0, 154.6, 147.4, 140.9, 137.5, 132.8, 129.6, 127.9, 126.5, 125.8, 109.9, 17.6, 16.3.IR (KBr, ν / cm-1): 2925, 2863, 1682, 1604, 1586, 1480, 1465, 1377, 1269, 1239, 1186, 1125, 1084, 1026, 922, 884, 827, 786, 739, 718.HRMS (ESI): calcd. for C14H14NO2 ([M+H]+ ): 228.1019, found: 228.1023.

11

O

O

N

MeMe

3-Methyl-2-((4-methylpyridin-2-yl)oxy)benzaldehyde (1u)White solid, M.p. 67 – 68 ℃, 1.56 g, 86%.1H NMR (300 MHz, CDCl3) δ 10.15 (d, J = 0.4 Hz, 1H), 7.94 (dd, J = 5.0, 2.5 Hz, 1H), 7.80 (d, J = 7.7 Hz, 1H), 7.52 (d, J = 6.9 Hz, 1H), 7.30 – 7.24 (m, 1H), 6.81 (d, J = 9.1 Hz, 2H), 2.37 (s, 3H), 2.16 (s, 3H).13C NMR (75 MHz, CDCl3) δ 189.8, 163.9, 154.4, 151.6, 147.2, 137.4, 132.7, 129.5, 126.4, 125.7, 120.1, 110.6, 21.2, 16.2.IR (KBr, ν / cm-1): 2956, 2858, 1698, 1682, 1611, 1588, 1564, 1467, 1390, 1289, 1250, 1188, 1149, 1085, 946, 923, 866, 819, 793, 781, 767, 734.HRMS (ESI): calcd. for C14H14NO2 ([M+H]+ ): 228.1019, found: 228.1028.

O

O

N

OMe

OMe

3-Methoxy-2-((5-methoxypyridin-2-yl)oxy)benzaldehyde (1v)White solid, M.p. 64 – 65 ℃, 1.43 g, 69%.1H NMR (300 MHz, CDCl3) δ 10.25 (d, J = 0.7 Hz, 1H), 7.72 (d, J = 3.1 Hz, 1H), 7.54 (ddd, J = 7.7, 1.6, 0.8 Hz, 1H), 7.35 – 7.18 (m, 3H), 7.00 (dd, J = 8.9, 0.5 Hz, 1H), 3.80 (s, 3H), 3.76 (s, 3H).13C NMR (75 MHz, CDCl3) δ 189.8, 158.0, 152.6, 152.4, 146.0, 132.1, 130.5, 126.8, 126.0, 119.5, 118.3, 110.9, 56.4, 56.2.IR (KBr, ν / cm-1): 2941, 2839, 1696, 1584, 1479, 1385, 1316, 1272, 1234, 1181, 1065, 1032, 1011, 886, 834, 774, 736, 715.HRMS (ESI): calcd. for C14H14NO4 ([M+H]+ ): 260.0917, found: 260.0928.

O

O

NF Me

5-Fluoro-2-((5-methylpyridin-2-yl)oxy)benzaldehyde (1w)Light yellow solid, M.p. 46 – 47 ℃, 1.24 g, 67%.1H NMR (300 MHz, CDCl3) δ 10.23 (d, J = 3.1 Hz, 1H), 7.95 (s, 1H), 7.67 – 7.53 (m, 2H), 7.38 – 7.26 (m, 1H), 7.15 (dd, J = 9.0, 4.3 Hz, 1H), 6.97 (d, J = 8.3 Hz, 1H), 2.29 (s, 3H).13C NMR (75 MHz, CDCl3) δ 188.3, 161.7, 159.5 (d, J = 246.3 Hz), 152.9 (d, J = 2.6

12

Hz), 147.3, 141.0, 129.7 (d, J = 6.3 Hz), 129.0, 124.4 (d, J = 7.6 Hz), 122.6 (d, J = 24.1 Hz), 114.1 (d, J = 23.7 Hz), 111.2, 17.6.19F NMR (376 MHz, CDCl3) δ -116.6 (s).IR (KBr, ν / cm-1): 3023, 2866, 1690, 1604, 1581, 1472, 1425, 1377, 1244, 1183, 1141, 1027, 964, 881, 824, 744, 698.HRMS (ESI): calcd. for C13H11FNO2 ([M+H]+ ): 232.0768, found: 232.0778.

O

O

N

2-(Isoquinolin-1-yloxy)benzaldehyde (1x)White solid. 15%, 0.3 g.1H NMR (300 MHz, CDCl3) δ 10.29 (s, 1H), 8.47 (d, J = 8.1 Hz, 1H), 8.03 (dd, J = 7.8, 1.7 Hz, 1H), 7.94 (d, J = 5.9 Hz, 1H), 7.85 (d, J = 7.6 Hz, 1H), 7.81 – 7.74 (m, 1H), 7.73 – 7.65 (m, 2H), 7.43 – 7.30 (m, 3H).13C NMR (101 MHz, CDCl3) δ 189.2, 160.7, 156.5, 139.8, 138.8, 135.7, 131.4, 129.2, 128.9, 127.8, 126.7, 125.8, 124.1, 123.6, 119.6, 117.4; 1H and 13C NMR data agreed with literature [4].

O

O

N

2-(Quinolin-2-yloxy)benzaldehyde (1y)Light yellow soild. 57%, 1.1 g.1H NMR (300 MHz, CDCl3) δ 10.32 (d, J = 0.7 Hz, 1H), 8.17 (d, J = 8.8 Hz, 1H), 8.00 (dd, J = 7.8, 1.7 Hz, 1H), 7.74 (dd, J = 17.3, 8.1 Hz, 2H), 7.68 – 7.56 (m, 2H), 7.43 (t, J = 7.5 Hz, 1H), 7.34 (td, J = 8.5, 4.6 Hz, 2H), 7.20 (d, J = 8.8 Hz, 1H).13C NMR (75 MHz, CDCl3) δ 189.3, 161.6, 156.3, 146.3, 140.5, 135.5, 130.2, 128.8, 128.7, 128.0, 127.6, 126.0, 125.4, 125.4, 123.1, 112.6; 1H and 13C NMR data agreed with literature [4].

O

O

CN

4-(2-Formylphenoxy)benzonitrile (1z)White solid, 0.89 g, 50%.1H NMR (300 MHz, CDCl3) δ 10.35 (d, J = 0.7 Hz, 1H), 7.99 (dd, J = 7.8, 1.8 Hz, 1H),

13

7.69 – 7.64 (m, 3H), 7.39 – 7.33 (m, 1H), 7.13 – 7.06 (m, 2H), 7.05 (dd, J = 8.3, 0.7 Hz, 1H).13C NMR (75 MHz, CDCl3) δ 188.6, 161.0, 157.4, 136.3, 134.6, 129.5, 128.0, 125.6, 120.7, 119.9, 118.6, 107.3; 1H and 13C NMR data agreed with literature [4].

O

O

CO2Me

Methyl 4-(2-formylphenoxy)benzoate (1aa)White solid, 0.80 g, 39%.1H NMR (300 MHz, CDCl3) δ 10.41 (d, J = 0.7 Hz, 1H), 8.09 – 8.03 (m, 2H), 7.97 (dd, J = 7.8, 1.8 Hz, 1H), 7.65 – 7.55 (m, 1H), 7.29 (dd, J = 8.3, 6.8 Hz, 1H), 7.12 – 6.98 (m, 3H), 3.91 (s, 3H).13C NMR (75 MHz, CDCl3) δ 188.9, 166.4, 161.0, 158.4, 136.1, 132.1, 128.9, 127.6, 125.7, 124.8, 120.1, 118.1, 52.3; 1H and 13C NMR data agreed with literature [4].

O

O

CF3

2-(4-(trifluoromethyl)phenoxy)benzaldehyde (1ab)Colorless oil, 0.92 g, 43%.1H NMR (400 MHz, CDCl3) δ 10.42 (s, 1H), 7.98 (dd, J = 7.8, 1.4 Hz, 1H), 7.69 – 7.51 (m, 3H), 7.30 (t, J = 7.5 Hz, 1H), 7.13 (d, J = 8.4 Hz, 2H), 6.99 (d, J = 8.3 Hz, 1H).13C NMR (101 MHz, CDCl3) δ 188.9, 159.9, 158.5, 136.2, 129.2, 127.8, 127.7 (q, J = 3.7 Hz), 126.3 (d, J = 33.0 Hz), 124.9, 124.2 (d, J = 271.7 Hz), 119.9, 118.7; 1H and 13C NMR data agreed with literature [5].

O

OF

2-(2-Fluorophenoxy)benzaldehyde (1ac)White solid, 0.94 g, 54%.1H NMR (300 MHz, CDCl3) δ 10.62 (d, J = 0.7 Hz, 1H), 7.94 (dd, J = 7.7, 1.8 Hz, 1H), 7.49 (ddd, J = 8.4, 7.3, 1.8 Hz, 1H), 7.25 – 7.11 (m, 5H), 6.79 (d, J = 8.4 Hz, 1H).13C NMR (75 MHz, CDCl3) δ 189.2, 160.1, 154.5 (d, J = 249.6 Hz), 142.7 (d, J = 11.2 Hz), 135.9, 128.6, 126.2 (d, J = 6.9 Hz), 125.9, 125.2 (d, J = 4.0 Hz), 123.3, 122.8, 117.5 (d, J = 18.0 Hz), 116.3; 1H and 13C NMR data agreed with literature [6].

14

O

OBr

Cl

2-(2-bromo-4-chlorophenoxy)benzaldehyde (1ad)

Colorless oil, 1.62 g, 65%.

1H NMR (400 MHz, CDCl3) δ 10.56 (s, 1H), 7.96 (dd, J = 7.7, 1.7 Hz, 1H), 7.66 (d, J = 2.3 Hz, 1H), 7.54 – 7.47 (m, 1H), 7.41 (dd, J = 8.7, 2.3 Hz, 1H), 7.22 (t, J = 7.5 Hz, 1H), 6.96 (d, J = 8.7 Hz, 1H), 6.74 (d, J = 8.3 Hz, 1H).13C NMR (101 MHz, CDCl3) δ 189.0, 159.2, 150.9, 136.0, 133.9, 131.6, 129.1, 127.8, 126.4, 124.0, 123.0, 118.0, 117.0.IR (KBr, ν / cm-1): 3125, 2919, 2873, 1690, 1652, 1601, 1541, 1469, 1456, 1396, 1258, 1236, 1197, 1132, 1079, 1057, 823, 760, 742.HRMS (ESI): calcd. for C13H9BrClO2 ([M+H]+ ): 312.9448, found: 312.9455.

O

OMe

Me

2-(2,6-Dimethylphenoxy)benzaldehyde (1ae)Light yellow solid, M.p. 62 – 63 ℃, 0.87 g, 48%.1H NMR (300 MHz, CDCl3) δ 10.78 (d, J = 0.7 Hz, 1H), 7.93 (dd, J = 7.7, 1.8 Hz, 1H), 7.49 – 7.33 (m, 1H), 7.19 – 7.11 (m, 3H), 7.07 (dd, J = 11.7, 4.2 Hz, 1H), 6.44 (d, J = 8.4 Hz, 1H), 2.15 (s, 6H).13C NMR (75 MHz, CDCl3) δ 189.5, 160.3, 150.4, 136.1, 131.3, 129.4, 128.7, 125.9, 124.4, 121.7, 115.3, 113.6, 16.5.IR (KBr, ν / cm-1): 2981, 2854, 1690, 1651, 1600, 1581, 1474, 1456, 1395, 1267, 1224, 1180, 1156, 1099, 1089, 1035, 876, 825, 800, 762.HRMS (ESI): calcd. for C15H15O2 ([M+H]+ ): 227.1607, found: 227.1068.

O

OOMe

2-(2-Methoxyphenoxy)benzaldehyde (1af)White solid, 0.84 g, 46%.1H NMR (300 MHz, CDCl3) δ 10.65 (d, J = 0.8 Hz, 1H), 7.91 (dd, J = 7.7, 1.8 Hz, 1H), 7.43 (ddd, J = 8.4, 7.3, 1.8 Hz, 1H), 7.21 (ddd, J = 8.1, 7.4, 1.8 Hz, 1H), 7.14 – 6.93

15

(m, 4H), 6.75 – 6.67 (m, 1H), 3.78 (s, 3H).13C NMR (75 MHz, CDCl3) δ 189.7, 161.0, 151.6, 143.8, 135.7, 128.1, 126.2, 125.6, 122.5, 122.1, 121.3, 116.3, 113.0, 55.9; 1H and 13C NMR data agreed with literature [2].

O

OOMe

OMe

2-(2,6-Dimethoxyphenoxy)benzaldehyde (1ag)White solid, M.p. 110 – 111 ℃, 1.09 g, 53%.1H NMR (300 MHz, CDCl3) δ 10.77 (d, J = 0.7 Hz, 1H), 7.89 (dd, J = 7.7, 1.8 Hz, 1H), 7.38 (ddd, J = 8.5, 7.3, 1.8 Hz, 1H), 7.18 (t, J = 8.4 Hz, 1H), 7.05 (t, J = 7.5 Hz, 1H), 6.72 – 6.55 (m, 3H), 3.77 (s, 6H).13C NMR (75 MHz, CDCl3) δ 190.1, 161.5, 153.5, 135.6, 132.0, 127.9, 126.2, 125.1, 121.9, 114.9, 109.9, 105.4, 56.3.IR (KBr, ν / cm-1): 2996, 2832, 1684, 1599, 1480, 1444, 1397, 1303, 1280, 1257, 1235, 1184, 1157, 1033, 875, 823, 799, 768, 750, 735, 701. HRMS (ESI): calcd. for C15H15O4 ([M+H]+ ): 259.0965, found: 259.0964.

IV. UV-vis absorption spectra of 1a

250 275 300 325 350 375 4000.00

0.25

0.50

0.75

1.00

Abs

orba

nce

(a. u

.)

Wavelength (nm)

C1a = 5.0 x 10-5 M

Figure S1 UV-vis absorption spectra of 1a

16

V. General procedures for heteroaryl/aryl rearrangement

i. General procedures for heteroaryl rearrangement

The starting materials 1 (0.2 mmol), TFA (0.2 mmol) were added into 2.0 mL of ethyl acetate in an airtight quartz tube, which was then evacuated by four freeze-pump-thaw cycles and back-filled with ultra-purified argon prior to use. The reaction was stirred at room temperature under UV irradiation (254 nm) for 24 h and 5 mL saturated NaHCO3 aqueous solution was added into the reaction solution, and extracted with 3 × 5 mL EtOAc. The combined organic phases were washed with brine, dried over anhydrous MgSO4 and concentrated under reduced pressure. Purification by column chromatography on silica (PE/EA = 20/1) affords 2.

ii. General procedures for aryl rearrangement

The starting materials 1 (0.2 mmol) were added into 2.0 mL of ethyl acetate in an airtight quartz tube, which was then evacuated by four freeze-pump-thaw cycles and back-filled with ultra-purified argon prior to use. The reaction was stirred at room temperature under UV irradiation (254 nm) for 24 h. The reaction mixture was concentrated under reduced pressure. Purification by column chromatography on silica (PE/EA = 30/1) affords 2.

VI. Characterization data of rearrangement products

OH

ON

(2-Hydroxyphenyl)(pyridin-2-yl)methanone (2a) Yellow oil. 33.1 mg, 83%.1H NMR (300 MHz, CDCl3) δ 12.36 (s, 1H), 8.73 (dt, J = 4.8, 1.4 Hz, 1H), 8.11 (dd, J = 8.1, 1.7 Hz, 1H), 7.96 – 7.89 (m, 2H), 7.56 – 7.47 (m, 2H), 7.06 (dd, J = 8.4, 0.7 Hz, 1H), 6.90 (ddd, J = 8.2, 7.2, 1.2 Hz, 1H). 13C NMR (75 MHz, CDCl3) δ 197.4, 163.6, 155.4, 148.4, 137.6, 136.8, 134.5, 126.3, 124.8, 119.3, 119.0, 118.6; 1H and 13C NMR data agreed with literature[4].

OH

O

N

Me

(2-Hydroxyphenyl)(3-methylpyridin-2-yl)methanone (2b)

17

Light yellow oil. 34.5 mg, 81%.1H NMR (300 MHz, CDCl3) δ 12.08 (s, 1H), 8.52 (dd, J = 4.7, 0.7 Hz, 1H), 7.67 (d, J = 7.8 Hz, 1H), 7.53 – 7.48 (m, 1H), 7.40 – 7.32 (m, 2H), 7.06 (dd, J = 8.4, 1.0 Hz, 1H), 6.88 – 6.76 (m, 1H), 2.37 (s, 3H).13C NMR (75 MHz, CDCl3) δ 200.6, 163.9, 154.4, 146.2, 139.2, 137.2, 133.7, 132.0, 124.8, 119.2, 119.1, 118.4, 18.2. IR (KBr, ν / cm-1): 3052, 2933, 1694, 1638, 1485, 1455, 1340, 1149, 1107, 1062, 1034, 944, 864, 795, 762.HRMS (ESI): calcd. for C13H12NO2 ([M+H]+ ): 214.0863, found: 214.0860.

OH

ON

Me

(2-Hydroxyphenyl)(4-methylpyridin-2-yl)methanone (2c)Yellow oil. 30.2 mg, 71%.1H NMR (300 MHz, CDCl3) δ 12.53 (s, 1H), 8.57 (d, J = 5.0 Hz, 1H), 8.09 (dd, J = 8.1, 1.7 Hz, 1H), 7.77 – 7.76 (m, 1H), 7.54 – 7.46 (m, 1H), 7.33 (ddd, J = 5.0, 1.6, 0.7 Hz, 1H), 7.05 (dd, J = 8.4, 1.1 Hz, 1H), 6.90 (ddd, J = 8.2, 7.2, 1.2 Hz, 1H), 2.47 (s, 3H).13C NMR (75 MHz, CDCl3) δ 197.5, 163.3, 155.2, 149.2, 148.0, 136.7, 134.4, 127.2, 125.5, 119.7, 119.0, 118.6, 21.4. IR (KBr, ν / cm-1): 3058, 2920, 1627, 1599, 1485, 1444, 1330, 1308, 1258, 1211, 1161, 954, 855, 807, 756, 661.HRMS (ESI): calcd. for C13H12NO2 ([M+H]+ ): 214.0863, found: 214.0861.

OH

ON

Me

(2-Hydroxyphenyl)(5-methylpyridin-2-yl)methanone (2d)Light yellow solid, M.p. 77 – 78 ℃. 38.3 mg, 90%.1H NMR (300 MHz, CDCl3) δ 12.51 (s, 1H), 8.54 (dd, J = 1.4, 0.6 Hz, 1H), 8.17 (dd, J = 8.1, 1.7 Hz, 1H), 7.88 (d, J = 8.0 Hz, 1H), 7.71 (ddd, J = 8.0, 2.1, 0.5 Hz, 1H), 7.49 (ddd, J = 8.8, 7.2, 1.7 Hz, 1H), 7.06 – 7.02 (m, 1H), 6.93 – 6.86 (m, 1H), 2.45 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 196.9, 163.3, 152.8, 148.7, 138.0, 136.9, 136.5, 134.4, 124.6, 119.6, 118.9, 118.6, 18.8. IR (KBr, ν / cm-1): 3037, 2926, 1627, 1567, 1477, 1491, 1381, 1336, 1318, 1148, 1142,

18

1084, 943, 849, 799, 786, 691.HRMS (ESI): calcd. for C13H12NO2 ([M+H]+ ): 214.0863, found: 214.0860.

OH

ON

OMe

(2-Hydroxyphenyl)(5-methoxypyridin-2-yl)methanone (2e)Yellow oil. 44.0 mg, 96%.1H NMR (300 MHz, CDCl3) δ 12.46 (s, 1H), 8.38 (d, J = 2.7 Hz, 1H), 8.31 (d, J = 8.1 Hz, 1H), 8.02 (d, J = 8.7 Hz, 1H), 7.49 (t, J = 7.1 Hz, 1H), 7.35 (dd, J = 8.7, 2.8 Hz, 1H), 7.04 (d, J = 8.3 Hz, 1H), 6.91 (t, J = 7.6 Hz, 1H), 3.95 (s, 3H).13C NMR (75 MHz, CDCl3) δ 195.8, 163.3, 157.8, 147.8, 136.4 (d, J = 4.4 Hz), 134.5, 126.7, 120.6, 119.5, 118.8, 118.4, 56.0. IR (KBr, ν / cm-1): 3013, 2970, 2942, 2844, 1623, 1570, 1477, 1442, 1395, 1272, 1148, 1026, 941, 829, 805, 758, 687. HRMS (ESI): calcd. for C13H12NO3 ([M+H]+ ): 230.0812, found: 230.0811.

OH

ON OMe

(2-Hydroxyphenyl)(6-methoxypyridin-2-yl)methanone (2f)Yellow oil. 26.1 mg, 57%.1H NMR (300 MHz, CDCl3) δ 12.24 (s, 1H), 8.27 (dd, J = 8.1, 1.7 Hz, 1H), 7.77 (dd, J = 8.3, 7.3 Hz, 1H), 7.56 – 7.45 (m, 2H), 7.06 (dd, J = 8.4, 1.1 Hz, 1H), 6.96 (dd, J = 8.4, 0.7 Hz, 1H), 6.93 – 6.85 (m, 1H), 3.97 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 197.5, 164.0, 163.0, 152.8, 139.5, 136.7, 134.4, 119.0, 118.6, 118.4, 118.0, 114.4, 54.0. IR (KBr, ν / cm-1): 3080, 3015, 2983, 2952, 2857, 1630, 1586, 1468, 1436, 1345, 1293, 1246, 1151, 1079, 971, 875, 825, 792, 730, 687. HRMS (ESI): calcd. for C13H12NO3 ([M+H]+ ): 230.0812, found: 230.0809.

OH

ON

F

(5-Fluoropyridin-2-yl)(2-hydroxyphenyl)methanone (2g)Yellow solid, M.p. 72 – 73 ℃. 34.7 mg, 80%.1H NMR (300 MHz, CDCl3) δ 12.12 (s, 1H), 8.58 (d, J = 2.6 Hz, 1H), 8.20 – 8.14 (m,

19

1H), 8.02 (dd, J = 8.7, 4.5 Hz, 1H), 7.62 (td, J = 8.3, 2.7 Hz, 1H), 7.52 (t, J = 7.1 Hz, 1H), 7.06 (d, J = 8.4 Hz, 1H), 6.92 (t, J = 7.4 Hz, 1H). 13C NMR (75 MHz, CDCl3) δ 196.0, 164.0, 160.7 (d, J = 263.3 Hz), 151.7, 137.0 (d, J = 24.2 Hz), 137.0, 134.5, 126.8 (d, J = 5.4 Hz), 124.2 (d, J = 18.5 Hz), 119.0, 118.6, 118.5. 19F NMR (376 MHz, CDCl3) δ -120.5 (dd, J = 8.0, 4.6 Hz).IR (KBr, ν / cm-1): 2918, 2875, 2853, 1627, 1584, 1566, 1513, 1384, 1261, 1224, 1181, 1149, 1049, 1034, 941, 872, 792, 751, 690. HRMS (ESI): calcd. for C12H9FNO2 ([M+H]+ ): 218.0612, found: 218.0611.

OH

ON

Cl

(5-Chloropyridin-2-yl)(2-hydroxyphenyl)methanone (2h)Light yellow solid, M.p. 89 – 90 ℃. 33.6 mg, 72%.1H NMR (300 MHz, CDCl3) δ 12.09 (s, 1H), 8.69 (s, 1H), 8.15 (d, J = 8.1 Hz, 1H), 7.91 (s, 2H), 7.53 (t, J = 7.8 Hz, 1H), 7.06 (d, J = 8.4 Hz, 1H), 6.91 (t, J = 7.6 Hz, 1H).

13C NMR (75 MHz, CDCl3) δ 196.3, 163.9, 153.3, 147.5, 137.3, 137.1, 135.2, 134.3, 125.8, 119.0, 118.5. IR (KBr, ν / cm-1): 3054, 2998, 2924, 2867, 1627, 1572, 1483, 1461, 1373, 1310, 1248, 1112, 1015, 941, 851, 825, 801, 754, 734, 730, 691. HRMS (ESI): calcd. for C12H9ClNO2 ([M+H]+ ): 234.0316, found: 234.0321.

OH

ON

Br

(5-bromopyridin-2-yl)(2-hydroxyphenyl)methanone (2i)Light yellow solid, M.p. 103 – 104 ℃. 37.3 mg, 67%.1H NMR (300 MHz, CDCl3) δ 12.07 (s, 1H), 8.79 (dd, J = 2.2, 0.6 Hz, 1H), 8.14 (dd, J = 8.1, 1.6 Hz, 1H), 8.05 (dd, J = 8.4, 2.3 Hz, 1H), 7.83 (dd, J = 8.4, 0.6 Hz, 1H), 7.52 (ddd, J = 8.7, 7.3, 1.6 Hz, 1H), 7.05 (dd, J = 8.4, 1.0 Hz, 1H), 6.90 (ddd, J = 8.2, 7.2, 1.2 Hz, 1H).13C NMR (75 MHz, CDCl3) δ 196.5, 163.9, 153.8, 149.7, 140.2, 137.1, 134.3, 126.1, 124.3, 119.1, 118.6, 118.5.IR (KBr, ν / cm-1): 3027, 2948, 2879, 1627, 1565, 1483, 1445, 1369, 1333, 1310, 1251,

20

1230, 1148, 1112, 1088, 1008, 940, 849, 824, 800, 755, 667. HRMS (ESI): calcd. for C12H9BrNO2 ([M+H]+ ): 277.9811, found: 277.9814.

OH

ON

CF3

(2-Hydroxyphenyl)(5-(trifluoromethyl)pyridin-2-yl)methanone (2j)Yellow oil. 25.1 mg, 47%.1H NMR (300 MHz, CDCl3) δ 11.97 (s, 1H), 9.01 (dd, J = 1.4, 0.7 Hz, 1H), 8.23 – 8.12 (m, 1H), 8.03 (ddd, J = 8.2, 3.6, 1.1 Hz, 2H), 7.55 (ddd, J = 8.5, 7.2, 1.7 Hz, 1H), 7.13 – 7.03 (m, 1H), 6.98 – 6.86 (m, 1H). 13C NMR (75 MHz, CDCl3) δ 196.5, 164.2, 158.5, 145.6 (q, J = 4.0 Hz), 137.5, 134.8 (q, J = 3.5 Hz), 134.3, 128.6 (d, J = 33.5 Hz), 124.4, 123.2 (d, J = 272.9 Hz), 119.2, 118.7, 118.4.19F NMR (376 MHz, CDCl3) δ -62.6 (s).IR (KBr, ν / cm-1): 3080, 2922, 1630, 1571, 1487, 1448, 1394, 1325, 1258, 1243, 1170, 1148, 1017, 943, 815, 786. HRMS (ESI): calcd. for C13H9F3NO2 ([M+H]+ ): 268.0580, found: 268.0583.

O

S

N

OH

Benzo[d]thiazol-2-yl(2-hydroxyphenyl)methanone (2k)Yellow solid, M.p. 89 – 90 ℃. 29.2 mg, 57%.1H NMR (300 MHz, CDCl3) δ 12.10 (s, 1H), 9.25 (dd, J = 8.2, 1.7 Hz, 1H), 8.29 – 8.18 (m, 1H), 8.04 – 7.95 (m, 1H), 7.65 – 7.50 (m, 3H), 7.10 – 6.98 (m, 2H). 13C NMR (75 MHz, CDCl3) δ 187.8, 167.2, 164.3, 153.8, 137.7, 136.9, 134.2, 128.0, 127.3, 125.9, 122.3, 119.7, 118.6, 118.3; 1H and 13C NMR data agreed with literature [4].

OH

O

N

N Me

Me

(3,6-Dimethylpyrazin-2-yl)(2-hydroxyphenyl)methanone (2l)Light yellow oil. 36.9 mg, 81%.1H NMR (300 MHz, CDCl3) δ 11.93 (s, 1H), 8.52 (s, 1H), 7.54 (ddd, J = 8.6, 7.2, 1.7 Hz, 1H), 7.30 (dd, J = 8.0, 1.7 Hz, 1H), 7.08 (dd, J = 8.5, 1.0 Hz, 1H), 6.85 (ddd, J =

21

8.2, 7.2, 1.1 Hz, 1H), 2.60 (s, 3H), 2.55 (s, 3H).13C NMR (75 MHz, CDCl3) δ 199.4, 164.1, 150.1, 148.8, 148.6, 144.9, 137.7, 133.5, 119.3, 118.9, 118.7, 21.2, 21.1.IR (KBr, ν / cm-1): 3047, 3067, 2929, 2858, 1630, 1576, 1485, 1448, 1371, 1254, 1215, 1138, 1108, 1034, 1004, 952, 885, 864, 820, 756, 736, 691. HRMS (ESI): calcd. for C13H13N2O2 ([M+H]+ ): 229.0972, found: 229.0971.

OH

ON

Me

(2-Hydroxy-4-methylphenyl)(pyridin-2-yl)methanone (2m)Light yellow solid, M.p. 32 – 33 ℃. 32.4 mg, 76%.1H NMR (300 MHz, CDCl3) δ 12.38 (s, 1H), 8.72 (d, J = 4.7 Hz, 1H), 7.99 (d, J = 8.3 Hz, 1H), 7.91 (d, J = 3.7 Hz, 2H), 7.49 (dd, J = 8.9, 4.7 Hz, 1H), 6.86 (s, 1H), 6.72 (d, J = 8.3 Hz, 1H), 2.37 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 196.9, 163.9, 155.6, 148.7, 148.4, 137.5, 134.3, 126.1, 124.6, 120.4, 118.6, 116.8, 22.2. IR (KBr, ν / cm-1): 3060, 2985, 2924, 1641, 1584, 1556, 1504, 1345, 1308, 1261, 1171, 1047, 997, 870, 793, 785, 703. HRMS (ESI): calcd. for C13H12NO2 ([M+H]+ ): 214.0863, found: 214.0869.

OH

ON

Me

(2-Hydroxy-3-methylphenyl)(pyridin-2-yl)methanone (2n)Yellow solid, M.p. 42 – 45 ℃. 36.2 mg, 85%.1H NMR (300 MHz, CDCl3) δ 12.53 (s, 1H), 8.72 (dd, J = 4.9, 1.0 Hz, 1H), 7.94 – 7.88 (m, 3H), 7.51 – 7.46 (m, 1H), 7.38 (d, J = 7.2 Hz, 1H), 6.80 (t, J = 7.7 Hz, 1H), 2.31 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 198.1, 162.2, 155.7, 148.5, 137.6, 137.4, 132.0, 127.4, 126.0, 124.6, 118.3, 118.2, 15.9. IR (KBr, ν / cm-1): 3056, 3015, 2955, 2922, 1623, 1584, 1479, 1423, 1340, 1304, 1258, 1194, 1032, 995, 853, 780, 751, 687. HRMS (ESI): calcd. for C13H12NO2 ([M+H]+ ): 214.0863, found: 214.0871.

22

OH

ON

OMe

(2-Hydroxy-3-methoxyphenyl)(pyridin-2-yl)methanone (2o)Yellow solid, M.p. 85 – 86 ℃. 23.4 mg, 51%. 1H NMR (300 MHz, CDCl3) δ 12.78 (s, 1H), 8.73 (d, J = 4.8 Hz, 1H), 8.01 – 7.87 (m, 2H), 7.69 (dd, J = 8.3, 1.2 Hz, 1H), 7.58 – 7.49 (m, 1H), 7.11 (d, J = 8.0 Hz, 1H), 6.86 (t, J = 8.1 Hz, 1H), 3.94 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 197.3, 155.3, 153.7, 149.2, 148.2, 137.7, 126.4, 125.5, 124.8, 119.9, 118.4, 117.3, 56.4. IR (KBr, ν / cm-1): 3054, 3009, 2924, 2851, 1630, 1586, 1453, 1436, 1340, 1310, 1254, 1194, 1079, 985, 842, 803, 784, 747, 698.HRMS (ESI): calcd. for C13H12NO3 ([M+H]+ ): 230.0812, found: 230.0816.

OH

ONBr

(5-bromo-2-hydroxyphenyl)(pyridin-2-yl)methanone (2p)Yellow solid, M.p. 69 – 70 ℃. 43.4 mg, 78%.1H NMR (300 MHz, CDCl3) δ 12.63 (s, 1H), 8.75 – 8.73(m, 1H), 8.37 (d, J = 2.5 Hz, 1H), 8.04 – 7.92 (m, 2H), 7.59 – 7.54 (m, 2H), 6.96 (d, J = 8.9 Hz, 1H).13C NMR (75 MHz, CDCl3) δ 195.3, 162.1, 154.6, 148.2, 139.3, 138.0, 136.4, 126.9, 125.1, 121.1, 120.8, 110.7.IR (KBr, ν / cm-1): 3081, 2996, 1627, 1604, 1584, 1566, 1460, 1433, 1383, 1332, 1283, 1332, 1283, 1236, 1152, 1094, 1047, 1022, 995, 947, 901, 828, 750, 676. HRMS (ESI): calcd. for C12H9BrNO2 ([M+H]+ ): 277.9811, found: 277.9815.

OH

ONF

(5-Fluoro-2-hydroxyphenyl)(pyridin-2-yl)methanone (2q)Yellow solid, M.p. 48 – 49 ℃. 35.6 mg, 82%.1H NMR (300 MHz, CDCl3) δ 12.33 (s, 1H), 8.74 (d, J = 4.7 Hz, 1H), 8.05 – 7.99 (m, 2H), 7.95 (td, J = 7.7, 1.7 Hz, 1H), 7.55 (ddd, J = 7.3, 4.8, 1.4 Hz, 1H), 7.30 – 7.21 (m, 1H), 7.02 (dd, J = 9.1, 4.6 Hz, 1H). 13C NMR (75 MHz, CDCl3) δ 195.5, 159.6, 154.9 (d, J = 237.3 Hz), 154.8, 148.2,

23

137.9, 126.8, 125.0, 124.4 (d, J = 24.0 Hz), 119.9 (d, J = 7.4 Hz), 119.2 (d, J = 24.5 Hz), 119.2.19F NMR (376 MHz, CDCl3) δ -124.3 (ddd, J = 9.8, 7.6, 4.6 Hz).IR (KBr, ν / cm-1): 3093, 3060, 2920, 1641, 1615, 1584, 1485, 1422, 1343, 1284, 1252, 1138, 995, 980, 874, 833, 790, 672. HRMS (ESI): calcd. for C12H9FNO2 ([M+H]+ ): 218.0612, found: 218.0611.

OH

ONCl

(5-Chloro-2-hydroxyphenyl)(pyridin-2-yl)methanone (2r)Yellow solid, M.p. 42 – 43 ℃. 36.8 mg, 79%.1H NMR (300 MHz, CDCl3) δ 12.60 (s, 1H), 8.75 (d, J = 4.8 Hz, 1H), 8.24 (d, J = 2.7 Hz, 1H), 8.07 – 7.90 (m, 2H), 7.63 – 7.53 (m, 1H), 7.44 (dd, J = 8.9, 2.6 Hz, 1H), 7.01 (d, J = 8.9 Hz, 1H). 13C NMR (75 MHz, CDCl3) δ 195.4, 161.7, 154.6, 148.2, 138.0, 136.5, 133.4, 126.9, 125.1, 123.7, 120.3, 120.2. IR (KBr, ν / cm-1): 3019, 2968, 2920, 2799, 1632, 1587, 1567, 1463, 1435, 1390, 1336, 1287, 1237, 1157, 1130, 1025, 997, 874, 833, 752, 730, 692. HRMS (ESI): calcd. for C12H9ClNO2 ([M+H]+ ): 234.0316, found: 234.0316.

OH

ON

OMeMe

(2-Hydroxy-3-methylphenyl)(5-methoxypyridin-2-yl)methanone (2s)Yellow solid, M.p. 65 – 66 ℃. 46.2 mg, 95%.1H NMR (300 MHz, CDCl3) δ 12.63 (s, 1H), 8.38 (d, J = 2.9 Hz, 1H), 8.09 (dd, J = 8.2, 1.7 Hz, 1H), 7.97 (d, J = 8.7 Hz, 1H), 7.34 (dt, J = 8.8, 4.3 Hz, 2H), 6.86 – 6.73 (m, 1H), 3.93 (s, 3H), 2.30 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 196.5, 162.0, 157.6, 148.1, 137.2, 136.5, 132.1, 127.2, 126.5, 120.4, 118.5, 118.1, 55.9, 15.9. IR (KBr, ν / cm-1): 3054, 2976, 2929, 2845, 1619, 1578, 1476, 1423, 1341, 1306, 1267, 1241, 1135, 1039, 1023, 978, 874, 853, 814, 740, 704. HRMS (ESI): calcd. for C14H14NO3 ([M+H]+ ): 244.0968, found: 244.0971.

24

OH

ON

MeMe

(2-Hydroxy-3-methylphenyl)(5-methylpyridin-2-yl)methanone (2t)Yellow solid, M.p. 43 – 44 ℃. 40.4 mg, 89%.1H NMR (300 MHz, CDCl3) δ 12.63 (s, 1H), 8.54 (dd, J = 1.4, 0.7 Hz, 1H), 7.95 (ddd, J = 8.2, 1.7, 0.5 Hz, 1H), 7.82 (d, J = 8.0 Hz, 1H), 7.73 – 7.65 (m, 1H), 7.37 (d, J = 7.2 Hz, 1H), 6.85 – 6.72 (m, 1H), 2.44 (s, 3H), 2.31 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 197.8, 162.0, 153.0, 148.9, 137.7, 137.4, 136.5, 132.0, 127.3, 124.4, 118.5, 118.2, 18.8, 15.9. IR (KBr, ν / cm-1): 3025, 3012, 2931, 1633, 1575, 1497, 1412, 1367, 1304, 1222, 1180, 1032, 995, 853, 789, 751, 686. HRMS (ESI): calcd. for C14H14NO2 ([M+H]+ ): 228.1019, found: 228.1027.

OH

ON

MeMe

(2-Hydroxy-3-methylphenyl)(4-methylpyridin-2-yl)methanone (2u)Yellow oil. 30.9 mg, 68%.1H NMR (300 MHz, CDCl3) δ 12.62 (s, 1H), 8.57 (d, J = 5.0 Hz, 1H), 7.88 (ddd, J = 8.1, 1.1, 0.5 Hz, 1H), 7.76 – 7.66 (m, 1H), 7.39 – 7.35 (m, 1H), 7.30 (ddd, J = 5.0, 1.6, 0.7 Hz, 1H), 6.80 (t, J = 7.7 Hz, 1H), 2.46 (s, 3H), 2.31 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 198.3, 162.0, 155.5, 148.9, 148.2, 137.5, 132.0, 127.4, 126.9, 125.3, 118.5, 118.3, 21.3, 15.9. IR (KBr, ν / cm-1): 3054, 2955, 2924, 1620, 1599, 1559, 1477, 1451, 1425, 1330, 1256, 1170, 1086, 1051, 997, 812, 799, 783, 751, 697.HRMS (ESI): calcd. for C14H14NO2 ([M+H]+ ): 228.1019, found: 228.1023.

OH

ON

OMeOMe

(2-Hydroxy-3-methoxyphenyl)(5-methoxypyridin-2-yl)methanone (2v)Yellow solid, M.p. 88 – 89 ℃. 28.0 mg, 54%.1H NMR (300 MHz, CDCl3) δ 12.83 (s, 1H), 8.37 (d, J = 2.9 Hz, 1H), 8.05 (d, J = 8.8 Hz, 1H), 7.87 (dd, J = 8.3, 1.3 Hz, 1H), 7.37 (dd, J = 8.8, 2.9 Hz, 1H), 7.09 (d, J = 7.9 Hz, 1H), 6.86 (t, J = 8.1 Hz, 1H), 3.96 (s, 3H), 3.93 (s, 3H).

25

13C NMR (75 MHz, CDCl3) δ 195.8, 157.9, 153.5, 149.1, 147.8, 136.2, 126.7, 125.6, 120.8, 120.1, 118.1, 116.9, 56.4, 56.0. IR (KBr, ν / cm-1): 3058, 3006, 2940, 2840, 1625, 1576, 1451, 1436, 1343, 1313, 1250, 1189, 1178, 985, 844, 779, 738, 687. HRMS (ESI): calcd. for C14H14NO4 ([M+H]+ ): 260.0917, found: 260.0917.

OH

ONF

Me

(5-Fluoro-2-hydroxyphenyl)(5-methylpyridin-2-yl)methanone (2w)Yellow solid, M.p. 81 – 82 ℃. 43.0 mg, 93%. 1H NMR (300 MHz, CDCl3) δ 12.52 (s, 1H), 8.57 – 8.52 (m, 1H), 8.07 (dd, J = 9.9, 3.2 Hz, 1H), 7.96 (d, J = 8.0 Hz, 1H), 7.81 – 7.68 (m, 1H), 7.33 – 7.17 (m, 1H), 7.00 (dd, J = 9.1, 4.7 Hz, 1H), 2.47 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 195.1, 159.4, 154.9 (d, J = 236.8 Hz), 152.2, 148.5, 138.3, 137.5, 124.9, 124.1 (d, J = 23.9 Hz), 119.9 (d, J = 7.4 Hz), 119.6 (d, J = 6.8 Hz), 119.2 (d, J = 24.7 Hz), 18.9.19F NMR (376 MHz, CDCl3) δ -124.5 (ddd, J = 9.8, 7.5, 4.7 Hz).IR (KBr, ν / cm-1): 3037, 2965, 2931, 1638, 1612, 1593, 1479, 1422, 1384, 1343, 1287, 1218, 1136, 1034, 976, 874, 833, 784, 728, 687. HRMS (ESI): calcd. for C13H11FNO2 ([M+H]+ ): 232.0768, found: 230.0777.

OH

O

CN

4-(2-Hydroxybenzoyl)benzonitrile (2z)Yellow solid, M.p. 121 – 122 ℃. 17.0 mg, 38%.1H NMR (300 MHz, CDCl3) δ 11.79 (s, 1H), 7.85 – 7.80 (m, 2H), 7.79 – 7.74 (m, 2H), 7.56 (ddd, J = 8.6, 7.3, 1.7 Hz, 1H), 7.45 (dd, J = 8.1, 1.6 Hz, 1H), 7.10 (dd, J = 8.4, 0.9 Hz, 1H), 6.90 (ddd, J = 8.2, 7.2, 1.1 Hz, 1H).13C NMR (151 MHz, CDCl3) δ 199.7, 163.4, 141.6, 137.2, 133.0, 132.2, 129.4, 119.0, 118.8, 118.5, 117.9, 115.3; 1H and 13C NMR data agreed with literature [4].

OH

O

CO2Me

Methyl 4-(2-hydroxybenzoyl)benzoate (2aa)

26

White solid, M.p. 97 – 98 ℃. 22.0 mg, 43%.1H NMR (300 MHz, CDCl3) δ 11.93 (s, 1H), 8.21 – 8.12 (m, 2H), 7.75 – 7.68 (m, 2H), 7.57 – 7.47 (m, 2H), 7.09 (ddd, J = 8.3, 1.1, 0.6 Hz, 1H), 6.89 (ddd, J = 8.2, 7.2, 1.1 Hz, 1H), 3.98 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 201.1, 167.0, 166.4, 163.5, 141.8, 137.0, 133.5, 133.0, 129.7, 129.1, 119.1, 118.8, 52.7; 1H and 13C NMR data agreed with literature [4].

OH

O

CF3

(2-Hydroxyphenyl)(4-(trifluoromethyl)phenyl)methanone (2ab)White solid, M.p. 49 – 50 ℃. 17.6 mg, 33%.1H NMR (300 MHz, CDCl3) δ 11.89 (s, 1H), 7.79 (s, 4H), 7.65 – 7.46 (m, 2H), 7.10 (dd, J = 8.4, 1.1 Hz, 1H), 6.90 (ddd, J = 8.2, 7.2, 1.1 Hz, 1H).13C NMR (101 MHz, CDCl3) δ 200.6, 163.6, 141.2, 137.2, 133.6 (d, J = 32.7 Hz), 133.5, 129.5, 125.6 (q, J = 3.7 Hz), 123.8 (d, J = 272.6 Hz), 119.2, 118.9, 118.9; 1H and 13C NMR data agreed with literature [8].

OH

O F

(2-Fluorophenyl)(2-hydroxyphenyl)methanone (2ac)Light yellow oil. 21.6 mg, 50%.1H NMR (300 MHz, CDCl3) δ 11.98 (s, 1H), 7.60 – 7.38 (m, 4H), 7.30 (td, J = 7.5, 1.0 Hz, 1H), 7.21 (ddd, J = 9.5, 8.4, 0.9 Hz, 1H), 7.07 (dd, J = 8.4, 1.1 Hz, 1H), 6.87 (ddd, J = 8.2, 7.2, 1.1 Hz, 1H).13C NMR (101 MHz, CDCl3) δ 198.7, 163.2, 159.3 (d, J = 251.5 Hz), 137.3, 133.6 (d, J = 2.2 Hz), 133.1 (d, J = 8.2 Hz), 130.1 (d, J = 2.9 Hz), 126.5 (d, J = 15.9 Hz), 124.6 (d, J = 3.6 Hz), 119.9, 119.2, 118.5, 116.5 (d, J = 21.3 Hz).19F NMR (376 MHz, CDCl3) δ -112.2 – -112.3 (m).IR (KBr, ν / cm-1): 3063, 2920, 2862, 1630, 1615, 1580, 1485, 1451, 1336, 1269, 1246, 1220, 1146, 937, 834, 816, 754, 685. HRMS (ESI): calcd. for C13H10FO2 ([M+H]+ ): 217.0659, found: 217.0663.

O

OH

Br

Cl

27

(2-Bromo-4-chlorophenyl)(2-hydroxyphenyl)methanone (2ad)

Light yellow oil. 27.4 mg, 44%.1H NMR (400 MHz, CDCl3) δ 11.83 (s, 1H), 7.68 (d, J = 1.8 Hz, 1H), 7.57 – 7.48 (m, 2H), 7.25 – 7.20 (m, 2H), 7.07 (dd, J = 8.4, 0.8 Hz, 1H), 6.84 (ddd, J = 8.1, 7.3, 1.1 Hz, 1H).13C NMR (101 MHz, CDCl3) δ 199.7, 163.4, 137.6, 136.4, 133.4, 133.0, 132.2, 130.3, 129.9, 124.9, 119.4, 119.3, 118.7.IR (KBr, ν / cm-1): 3085, 2971, 2851, 1628, 1579, 1485, 1454, 1371, 1337, 1308, 1243, 1219, 1148, 1114, 1084, 935, 833, 777, 757, 656.HRMS (ESI): calcd. for C13H9BrClO2 ([M+H]+ ): 312.9448, found: 312.9458.

O Me

Me

OH

(2,6-Dimethylphenyl)(2-hydroxyphenyl)methanone (2ae)White solid, M.p. 112 – 113 ℃. 25.8 mg, 57%.1H NMR (300 MHz, CDCl3) δ 12.32 (s, 1H), 7.55 – 7.45 (m, 1H), 7.31 – 7.23 (m, 1H), 7.17 (dd, J = 8.0, 1.7 Hz, 1H), 7.12 – 7.04 (m, 3H), 6.83 – 6.75 (m, 1H), 2.16 (s, 6H).13C NMR (101 MHz, CDCl3) δ 206.6, 163.1, 138.3, 137.2, 134.2, 132.8, 129.3, 127.8, 120.2, 119.5, 118.5, 19.5.IR (KBr, ν / cm-1): 3069, 3000, 2955, 2924, 1623, 1576, 1489, 1449, 1328, 1306, 1243, 1224, 1151, 1030, 933, 827, 780, 766, 730, 690. HRMS (ESI): calcd. for C15H15O2 ([M+H]+ ): 227.1067, found: 227.1071.

OH

O OMe

(2-Hydroxyphenyl)(2-methoxyphenyl)methanone (2af)Colorless oil. 18.3 mg, 40%.1H NMR (300 MHz, CDCl3) δ 12.20 (s, 1H), 7.53 – 7.44 (m, 2H), 7.32 (ddd, J = 13.3, 7.7, 1.7 Hz, 2H), 7.11 – 6.98 (m, 3H), 6.87 – 6.75 (m, 1H), 3.78 (s, 3H).13C NMR (101 MHz, CDCl3) δ 202.3, 163.1, 156.7, 136.7, 134.0, 132.0, 129.0, 127.9, 120.7, 120.3, 118.9, 118.2, 111.6, 55.8.IR (KBr, ν / cm-1): 3013, 2955, 2840, 1628, 1600, 1487, 1461, 1332, 1310, 1280, 1246, 1148, 1121, 1023, 944, 980, 827, 754, 687. HRMS (ESI): calcd. for C14H13O3 ([M+H]+ ): 229.0859, found: 229.0865.

28

O OMe

MeO

OH

(2,6-Dimethoxyphenyl)(2-hydroxyphenyl)methanone (2ag)White solid, M.p. 117 – 118 ℃. 20.1 mg, 39%.1H NMR (300 MHz, CDCl3) δ 12.16 (s, 1H), 7.50 – 7.43 (m, 1H), 7.38 (t, J = 8.4 Hz, 1H), 7.28 (dd, J = 8.0, 1.7 Hz, 1H), 7.02 (dd, J = 8.4, 1.0 Hz, 1H), 6.83 – 6.75 (m, 1H), 6.63 (d, J = 8.4 Hz, 2H), 3.73 (s, 6H).13C NMR (101 MHz, CDCl3) δ 201.5, 162.7, 157.5, 136.6, 133.2, 131.5, 121.1, 119.1, 118.1, 116.6, 104.1, 56.1.IR (KBr, ν / cm-1): 3011, 2963, 2842, 1630, 1593, 1474, 1448, 1332, 1306, 1254, 1220, 1146, 1112, 937, 758, 725, 678. HRMS (ESI): calcd. for C15H15O4 ([M+H]+ ): 259.0965, found: 259.0972.

29

VII. References

1. D. Maiti and S. L. Buchwald, J. Org. Chem. 2010, 75, 1791–1794.2. H. Rao, X. Ma, Q. Liu, Z. Li, S. Cao, and C.-J. Li, Adv. Synth. Catal. 2013, 355,

2191–2196.3. D. C. Fabry, M. A. Ronge, J. Zoller, and M. Rueping, Angew. Chem. Int. Ed. 2015,

54, 2801–2805.4. D. Janssen-Müller, S. Singha, F. Lied, K. Gottschalk, F. Glorius, Angew. Chem. Int.

Ed. 2017, 56, 6276–6279.5. X. Qian, J. Han, L. Wang, RSC Adv. 2016, 6, 89234–89237.6. M. Pettersson, B. M. Campbell, A. B. Dounay, D. L. Gray, L. Xie, C. J. O’Donnell,

N. C. Stratman, K. Zoski, E. Drummond, G. Bora, A. Probert, T. Whisman, Bioorg. Med. Chem. Lett. 2011, 21, 865–868.

7. X. Yang, H. Wang, X. Zhou, X. Li, Org. Biomol. Chem., 2016, 14, 5233–5237.8. F. Weng, C. Wang, B. Xu, Tetrahedron Lett., 2010, 51, 2593-2596.

30

VIII. Copies of the 1H, 19F and 13C NMR spectra

1H and 13C NMR spectra of compound 1a

-101234567891011121314f1 (ppm)

2.09

1.04

1.06

1.02

1.01

1.00

1.00

0.87

7.04

7.05

7.06

7.07

7.08

7.17

7.20

7.31

7.34

7.36

7.74

7.75

7.77

7.77

7.79

7.80

7.96

7.97

7.99

7.99

8.17

8.18

10.3

1

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

111.

9511

9.41

122.

6012

5.31

128.

6212

8.80

135.

7014

0.07

147.

87

156.

60

163.

52

189.

34

O

O

N

O

O

N

31

1H and 13C NMR spectra of compound 1b

-101234567891011121314f1 (ppm)

3.00

1.08

1.00

1.11

2.19

2.10

0.85

2.41

6.95

6.97

6.99

7.14

7.17

7.28

7.31

7.33

7.57

7.60

7.62

7.62

7.65

7.96

7.96

7.98

7.98

10.3

010

.30

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

16.1

0

119.

5412

1.93

122.

5812

4.99

128.

4212

8.74

135.

5914

0.36

144.

90

156.

9316

1.77

189.

38

O

O

N

Me

O

O

N

Me

32

1H and 13C NMR spectra of compound 1c

-101234567891011121314f1 (ppm)

3.00

2.08

1.03

0.97

1.03

2.04

1.00

2.39

6.87

6.89

7.14

7.14

7.17

7.17

7.28

7.31

7.33

7.60

7.62

7.64

7.95

7.97

8.02

8.04

10.3

110

.31

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

21.2

1

112.

1712

0.82

122.

4912

5.14

128.

5112

8.67

135.

68

147.

3615

1.75

156.

7916

3.76

189.

40O

O

N

Me

O

O

N

Me

33

1H and 13C NMR spectra of compound 1d

-101234567891011121314f1 (ppm)

3.00

0.99

0.98

1.14

1.98

1.89

0.82

2.30

6.95

6.97

7.11

7.14

7.27

7.27

7.30

7.32

7.32

7.56

7.56

7.58

7.58

7.59

7.61

7.61

7.61

7.63

7.64

7.94

7.95

7.97

7.98

7.99

7.99

7.99

8.00

10.3

4

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

17.7

1

111.

57

122.

0712

4.96

128.

4012

8.69

128.

9313

5.69

140.

8914

7.56

157.

1516

1.62

189.

47O

O

NMe

O

O

NMe

34

1H and 13C NMR spectra of compound 1e

-101234567891011121314f1 (ppm)

3.00

2.00

2.16

1.03

0.98

0.96

0.82

3.84

7.00

7.03

7.06

7.09

7.25

7.27

7.30

7.33

7.34

7.36

7.37

7.57

7.59

7.62

7.85

7.86

7.94

7.97

10.3

8

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

56.2

5

112.

8012

1.35

124.

6012

6.62

128.

0312

8.58

132.

8913

5.67

152.

9615

7.12

157.

67

189.

50

O

O

NOMe

O

O

NOMe

35

1H and 13C NMR spectra of compound 1f

-101234567891011121314f1 (ppm)

3.00

2.02

0.99

1.03

2.07

0.97

0.86

3.69

6.48

6.49

6.49

6.51

6.51

6.51

7.17

7.18

7.20

7.20

7.31

7.59

7.61

7.64

7.95

7.95

7.97

10.3

410

.34

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

53.6

8

102.

1910

5.17

122.

5412

5.12

128.

2912

8.75

135.

5014

1.97

156.

8216

1.99

163.

40

189.

50

O

O

N

OMe

O

O

N

OMe

36

1H and 13C NMR spectra of compound 1g

-101234567891011121314f1 (ppm)

1.00

0.99

1.06

1.03

1.05

2.03

1.00

7.05

7.06

7.08

7.09

7.13

7.13

7.16

7.16

7.32

7.32

7.32

7.34

7.37

7.37

7.37

7.49

7.50

7.51

7.52

7.52

7.53

7.54

7.55

7.61

7.62

7.64

7.64

7.64

7.64

7.66

7.67

7.96

7.96

7.98

7.99

8.00

8.01

10.3

010

.30

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

112.

8611

2.92

122.

3512

5.45

127.

5112

7.79

129.

1213

4.55

135.

76

146.

37

155.

0015

6.59

189.

22O

O

NF

O

O

NF

37

19F NMR spectra of compound 1g

-250-240-230-220-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60f1 (ppm)

-134

.80

1H and 13C NMR spectra of compound 1h

-101234567891011121314f1 (ppm)

1.04

1.10

1.09

1.15

1.01

1.03

1.00

0.98

7.02

7.03

7.05

7.05

7.15

7.15

7.18

7.18

7.34

7.36

7.38

7.62

7.62

7.65

7.65

7.67

7.68

7.70

7.71

7.73

7.73

7.74

7.96

7.96

7.98

7.99

8.09

8.09

8.09

8.10

10.2

610

.26

O

O

NCl

38

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

112.

87

122.

6612

5.71

126.

8412

8.63

129.

2713

5.75

139.

9014

6.20

156.

0216

1.91

189.

07

1H and 13C NMR spectra of compound 1i

-101234567891011121314f1 (ppm)

0.89

1.00

1.11

1.11

0.91

1.06

0.84

0.97

6.97

6.97

7.00

7.00

7.15

7.15

7.18

7.18

7.33

7.35

7.38

7.61

7.61

7.63

7.64

7.64

7.64

7.66

7.67

7.82

7.83

7.83

7.85

7.85

7.86

7.95

7.95

7.97

7.98

8.18

8.19

10.2

5

O

O

NCl

O

O

NBr

39

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

113.

4411

4.57

122.

6812

5.72

128.

6912

9.30

135.

7014

2.58

148.

5115

5.94

162.

39

189.

00

1H and 13C NMR spectra of compound 1j

-101234567891011121314f1 (ppm)

2.00

1.00

1.05

2.00

1.00

0.88

7.17

7.20

7.20

7.23

7.23

7.23

7.39

7.42

7.44

7.66

7.66

7.68

7.69

7.69

7.71

7.71

7.96

7.97

7.98

7.99

8.00

8.00

8.39

8.40

8.40

8.40

10.2

0

O

O

NCF3

O

O

NBr

40

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

111.

7712

2.76

123.

2012

6.25

128.

8012

9.81

135.

7913

7.35

145.

5314

5.56

155.

08

165.

66

188.

83

19F NMR spectra of compound 1j

-120-110-100-95-90-85-80-75-70-65-60-55-50-45-40-35-30-25-20-15-10-5051015f1 (ppm)

-61.

72

O

O

NCF3

41

1H and 13C NMR spectra of compound 1k

-101234567891011121314f1 (ppm)

1.00

3.08

2.99

1.00

7.28

7.28

7.31

7.31

7.33

7.34

7.37

7.38

7.40

7.40

7.41

7.41

7.41

7.42

7.43

7.43

7.44

7.46

7.46

7.47

7.48

7.49

7.51

7.51

7.68

7.68

7.69

7.70

7.70

7.70

7.71

7.71

7.71

7.72

7.73

7.73

7.73

7.73

7.74

7.99

8.00

8.02

8.02

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

121.

6212

2.07

122.

1012

4.70

126.

6412

6.83

127.

8512

9.43

132.

5513

6.01

148.

75

156.

30

171.

40

188.

21O

O S

N

O

O S

N

42

1H and 13C NMR spectra of compound 1l

-101234567891011121314f1 (ppm)

3.00

2.99

1.01

0.96

0.98

0.92

0.85

0.86

-0.0

0

2.30

2.64

7.15

7.15

7.17

7.18

7.32

7.33

7.33

7.35

7.37

7.38

7.38

7.60

7.61

7.63

7.63

7.63

7.64

7.66

7.66

7.95

7.96

7.98

7.98

8.07

10.2

510

.25

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

19.0

420

.65

122.

5812

5.41

128.

5212

9.20

135.

5213

8.01

141.

3614

8.71

155.

8815

7.31

189.

05O

ON

N

Me

Me

O

ON

N

Me

Me

43

1H and 13C NMR spectra of compound 1m

-101234567891011121314f1 (ppm)

3.00

0.93

2.04

1.06

1.09

1.05

1.06

1.05

2.41

6.97

6.97

7.03

7.03

7.03

7.04

7.05

7.05

7.05

7.06

7.06

7.06

7.07

7.12

7.12

7.15

7.15

7.75

7.76

7.76

7.85

7.88

8.16

8.17

8.18

8.19

10.2

310

.23

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

22.1

0

111.

8711

9.24

122.

8712

6.23

126.

4112

8.72

139.

9914

7.30

147.

84

156.

52

163.

57

188.

99O

O

N

Me

O

O

N

Me

44

1H and 13C NMR spectra of compound 1n

-101234567891011121314f1 (ppm)

3.00

2.00

0.97

0.99

0.98

0.92

0.87

0.90

2.17

6.97

6.99

6.99

6.99

7.00

7.01

7.01

7.02

7.02

7.04

7.05

7.05

7.30

7.53

7.53

7.71

7.71

7.73

7.74

7.74

7.74

7.80

8.08

8.08

8.09

8.10

8.10

10.1

510

.16

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

16.2

9

110.

5711

8.69

125.

9212

6.63

129.

5213

2.79

137.

5214

0.02

147.

8315

4.33

163.

66

189.

85O

O

N

Me

O

O

N

Me

45

1H and 13C NMR spectra of compound 1o

-101234567891011121314f1 (ppm)

3.00

1.03

0.96

1.01

1.01

0.98

1.01

0.96

0.87

3.77

6.98

7.00

7.00

7.00

7.02

7.05

7.08

7.23

7.25

7.26

7.30

7.32

7.54

7.55

7.57

7.57

7.73

7.73

8.08

8.09

8.10

8.11

10.2

410

.24

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

56.3

7

110.

7111

8.23

118.

7911

9.62

126.

2113

0.30

139.

7514

5.47

147.

5715

2.47

163.

67

189.

68

O

O

N

OMe

O

O

N

OMe

46

1H and 13C NMR spectra of compound 1p

-101234567891011121314f1 (ppm)

3.00

0.93

1.07

0.90

1.03

0.87

7.06

7.06

7.07

7.08

7.09

7.09

7.11

7.69

7.70

7.72

7.73

8.06

8.07

8.14

8.15

8.16

10.2

1

0102030405060708090100110120130140150160170180190200210220230240f1 (ppm)

111.

9911

8.57

119.

7412

4.68

130.

0213

1.39

138.

2414

0.24

147.

7915

5.47

163.

15

187.

86O

O

NBr

O

O

NBr

47

1H and 13C NMR spectra of compound 1q

-101234567891011121314f1 (ppm)

2.04

1.00

1.03

0.98

1.02

1.00

0.99

7.04

7.04

7.06

7.06

7.07

7.08

7.09

7.17

7.18

7.20

7.21

7.30

7.32

7.33

7.33

7.34

7.34

7.36

7.37

7.61

7.62

7.63

7.65

7.74

7.75

7.77

7.77

7.77

7.78

7.79

7.80

8.13

8.13

8.14

8.14

8.15

8.15

8.16

10.2

110

.22

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

111.

7211

4.13

114.

4511

9.49

122.

5312

2.85

124.

7812

4.88

129.

8812

9.96

140.

1714

7.72

152.

3915

8.07

161.

3416

3.52

188.

18O

O

NF

O

O

NF

48

19F NMR spectra of compound 1q

-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10010f1 (ppm)

-116

.11

1H and 13C NMR spectra of compound 1r

-101234567891011121314f1 (ppm)

2.09

1.00

1.03

1.04

0.97

1.00

0.89

7.05

7.06

7.06

7.07

7.07

7.08

7.08

7.09

7.09

7.14

7.17

7.55

7.55

7.55

7.56

7.57

7.58

7.58

7.59

7.75

7.75

7.75

7.76

7.77

7.78

7.78

7.80

7.80

7.81

7.91

7.92

8.14

8.14

8.15

8.16

8.16

8.16

10.2

310

.23

O

O

NCl

O

O

NF

49

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

111.

9411

9.69

124.

3812

8.26

129.

6513

1.08

135.

3414

0.22

147.

7515

4.90

163.

21

187.

95

1H and 13C NMR spectra of compound 1s

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

16.3

0

56.2

8

110.

78

125.

7612

6.50

127.

2112

9.73

132.

2713

2.86

137.

51

152.

2715

4.84

158.

06

190.

01O

O

NCl

O

O

N

Me

OMe

50

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

16.3

0

56.2

8

110.

78

125.

7612

6.50

127.

2112

9.73

132.

2713

2.86

137.

51

152.

2715

4.84

158.

06

190.

01

1H and 13C NMR spectra of compound 1t

-2-101234567891011121314f1 (ppm)

3.07

3.00

0.96

1.06

1.96

0.98

0.93

0.88

2.16

2.26

6.90

6.93

7.26

7.26

7.27

7.28

7.31

7.52

7.54

7.79

7.82

7.89

7.89

10.1

510

.15

O

O

N

Me

Me

O

O

N

Me

OMe

51

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

16.2

917

.62

109.

86

125.

7912

6.52

127.

8812

9.63

132.

8313

7.50

140.

8614

7.38

154.

6216

2.04

189.

96

1H and 13C NMR spectra of compound 1u

-101234567891011121314f1 (ppm)

3.00

2.99

1.91

0.98

0.89

0.92

0.91

0.74

2.16

2.37

6.80

6.83

7.24

7.25

7.26

7.28

7.29

7.30

7.51

7.53

7.79

7.82

7.92

7.93

7.94

7.95

10.1

510

.15

O

O

N

Me

Me

O

O

N

MeMe

52

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

16.2

321

.15

110.

59

120.

0612

5.74

126.

4012

9.47

132.

7413

7.42

147.

2415

1.57

154.

42

163.

93

189.

83

1H and 13C NMR spectra of compound 1v

-101234567891011121314f1 (ppm)

3.00

2.99

1.01

3.03

0.99

0.97

0.94

3.76

3.80

6.98

6.98

7.01

7.01

7.23

7.24

7.27

7.30

7.30

7.31

7.31

7.32

7.34

7.52

7.53

7.53

7.55

7.55

7.56

7.72

7.73

10.2

510

.26

O

O

N

MeMe

O

O

N

OMe

OMe

53

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

56.2

456

.39

110.

9011

8.27

119.

5412

5.98

126.

8113

0.48

132.

08

146.

0215

2.36

152.

6015

8.03

189.

80

1H and 13C NMR spectra of compound 1w

-101234567891011121314f1 (ppm)

3.00

0.96

0.97

1.07

1.93

0.95

0.89

2.29

6.95

6.98

7.13

7.14

7.16

7.17

7.27

7.28

7.29

7.30

7.31

7.31

7.31

7.31

7.33

7.34

7.56

7.57

7.59

7.62

7.63

7.95

10.2

310

.24

O

O

N

OMe

OMe

O

O

NF Me

54

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

17.6

4

111.

2311

3.97

114.

2912

2.48

122.

8012

4.36

124.

4612

8.96

129.

6812

9.76

140.

9614

7.34

152.

8915

7.87

161.

1416

1.68

188.

29

19F NMR spectra of compound 1w

-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10010f1 (ppm)

-116

.55

O

O

NF Me

O

O

NF Me

55

1H and 13C NMR spectra of compound 1x

-101234567891011121314f1 (ppm)

3.18

2.28

1.12

1.06

0.99

1.02

1.00

0.96

7.31

7.34

7.37

7.39

7.40

7.42

7.65

7.66

7.67

7.68

7.68

7.69

7.70

7.70

7.71

7.72

7.72

7.75

7.75

7.78

7.78

7.80

7.80

7.84

7.86

7.93

7.95

8.01

8.02

8.04

8.04

8.46

8.49

10.2

9

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

117.

3811

9.58

123.

6312

4.10

125.

7912

6.67

127.

8012

8.97

129.

1613

1.41

135.

6813

8.85

139.

8015

6.46

160.

72

189.

19

O

O

N

O

O

N

56

1H and 13C NMR spectra of compound 1y

-101234567891011121314f1 (ppm)

0.96

2.04

1.07

2.09

1.98

1.00

1.00

1.00

7.19

7.22

7.29

7.32

7.32

7.35

7.37

7.38

7.40

7.43

7.45

7.57

7.60

7.62

7.62

7.64

7.64

7.65

7.66

7.67

7.67

7.67

7.70

7.73

7.76

7.78

7.98

7.99

8.01

8.02

8.16

8.19

10.3

210

.32

0102030405060708090100110120130140150160170180190200210220230f1 (ppm)

112.

5612

3.08

125.

3812

5.42

127.

5712

8.02

128.

7113

0.17

135.

5114

0.49

156.

2516

1.60

189.

26O

O

N

O

O

N

57

1H and 13C NMR spectra of compound 1z

-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.012.5f1 (ppm)

0.94

2.15

1.06

3.21

1.00

0.90

7.03

7.04

7.06

7.06

7.07

7.08

7.08

7.09

7.09

7.10

7.11

7.12

7.12

7.13

7.33

7.33

7.34

7.36

7.38

7.38

7.39

7.61

7.62

7.62

7.62

7.64

7.64

7.64

7.65

7.65

7.65

7.66

7.66

7.66

7.67

7.67

7.67

7.68

7.69

7.69

7.69

7.70

7.71

7.72

7.98

7.98

8.00

8.01

10.3

510

.36

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

107.

2611

8.64

119.

8512

0.66

125.

5612

7.97

129.

4613

4.59

136.

26

157.

3616

0.97

188.

57

O

O

CN

O

O

CN

58

1H and 13C NMR spectra of compound 1aa

-101234567891011121314f1 (ppm)

3.00

3.14

1.09

1.01

1.01

2.08

0.86

3.91

7.00

7.03

7.05

7.06

7.08

7.08

7.29

7.29

7.32

7.57

7.58

7.60

7.63

7.96

7.96

7.98

7.99

8.05

8.06

8.07

8.08

8.09

10.4

110

.42

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

52.2

9

118.

0512

0.09

124.

7712

5.71

127.

6312

8.93

132.

0513

6.09

158.

3816

0.96

166.

40

188.

94

O

O

CO2Me

O

O

CO2Me

59

1H and 13C NMR spectra of compound 1ab

-1.00.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.5f1 (ppm)

1.00

1.98

1.09

3.01

0.95

0.89

6.98

7.00

7.11

7.14

7.28

7.30

7.32

7.57

7.58

7.59

7.61

7.62

7.63

7.65

7.97

7.97

7.99

7.99

10.4

2

0102030405060708090100110120130140150160170180190200210f1 (ppm)

118.

7211

9.96

122.

8012

5.50

126.

1412

6.47

127.

6512

7.68

127.

7212

7.76

127.

8012

9.19

136.

15

158.

5115

9.89

188.

93

O

O

CF3

O

O

CF3

60

1H and 13C NMR spectra of compound 1ac

-101234567891011121314f1 (ppm)

1.00

5.18

1.07

1.00

0.84

6.77

6.80

7.13

7.14

7.15

7.16

7.16

7.17

7.18

7.18

7.19

7.20

7.20

7.21

7.22

7.22

7.23

7.23

7.24

7.24

7.25

7.46

7.47

7.49

7.49

7.49

7.50

7.51

7.52

7.93

7.93

7.95

7.96

10.6

110

.62

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

116.

3111

7.42

117.

6612

2.80

123.

3012

5.16

125.

2112

5.92

126.

1812

6.27

128.

6313

5.88

142.

5914

2.74

152.

8415

6.15

160.

10

189.

21

O

OF

O

OF

61

1H and 13C NMR spectra of compound 1ad

-3-2-1012345678910111213141516f1 (ppm)

0.96

1.00

1.05

1.00

1.07

0.92

0.98

0.87

6.73

6.75

6.95

6.97

7.20

7.22

7.24

7.40

7.40

7.42

7.43

7.49

7.49

7.51

7.51

7.53

7.53

7.66

7.67

7.94

7.95

7.96

7.97

10.5

6

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

117.

0311

7.99

122.

9912

3.97

126.

4012

7.75

129.

0613

1.55

133.

8813

5.97

150.

96

159.

21

189.

00

O

OBr

Cl

O

OBr

Cl

62

1H and 13C NMR spectra of compound 1ae

-101234567891011121314f1 (ppm)

6.00

1.06

1.15

3.06

1.09

1.06

0.93

2.15

6.43

6.45

7.07

7.09

7.09

7.12

7.13

7.13

7.37

7.39

7.40

7.92

7.92

7.94

7.95

10.7

810

.78

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

16.5

0

113.

6111

5.26

121.

7012

4.43

125.

8812

8.71

129.

3913

1.32

136.

13

150.

37

160.

32

189.

54O

OMe

Me

O

OMe

Me

63

1H and 13C NMR spectra of compound 1af

-101234567891011121314f1 (ppm)

3.00

1.10

4.23

1.06

1.14

1.10

0.95

3.78

6.70

6.70

6.70

6.73

6.73

6.97

6.97

7.00

7.01

7.02

7.04

7.04

7.05

7.06

7.08

7.09

7.10

7.21

7.43

7.89

7.90

7.92

7.92

10.6

410

.65

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

55.9

0

112.

9811

6.34

121.

3212

2.10

122.

4612

5.58

126.

1512

8.14

135.

7214

3.79

151.

61

160.

96

189.

74O

OOMe

O

OOMe

64

1H and 13C NMR spectra of compound 1ag

-101234567891011121314f1 (ppm)

6.00

3.15

1.05

1.04

1.05

1.00

0.86

3.77

6.62

6.62

6.65

6.65

6.68

7.02

7.05

7.07

7.15

7.18

7.21

7.35

7.36

7.38

7.38

7.38

7.39

7.40

7.41

7.87

7.88

7.90

7.90

10.7

710

.77

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

56.2

5

105.

3610

9.87

114.

9012

1.94

125.

0812

6.15

127.

8513

1.99

135.

59

153.

48

161.

46

190.

13

O

OOMe

OMe

O

OOMe

OMe

65

1H and 13C NMR spectra of compound 2a

-101234567891011121314f1 (ppm)

1.00

0.96

1.97

1.93

0.96

0.94

0.85

6.88

6.88

6.90

6.90

6.91

6.93

6.93

7.04

7.04

7.07

7.07

7.48

7.49

7.49

7.50

7.51

7.51

7.51

7.52

7.52

7.52

7.53

7.54

7.54

7.89

7.90

7.92

7.93

7.93

7.94

7.94

7.95

7.96

8.10

8.10

8.12

8.13

8.72

8.73

8.73

8.74

8.74

8.75

12.3

6

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

118.

5911

9.01

119.

2612

4.75

126.

2813

4.45

136.

8213

7.60

148.

3715

5.41

163.

55

197.

35

OH

ON

OH

ON

66

1H and 13C NMR spectra of compound 2b

-1.00.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.513.5f1 (ppm)

3.00

1.08

1.02

2.10

1.07

1.04

0.98

0.88

2.37

6.80

6.80

6.83

6.85

6.85

7.04

7.05

7.07

7.07

7.33

7.33

7.35

7.36

7.38

7.48

7.48

7.50

7.50

7.51

7.66

7.69

8.51

8.51

8.53

8.53

12.0

8

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

18.1

9

118.

4311

9.13

119.

1812

4.81

131.

9813

3.72

137.

1513

9.16

146.

2415

4.41

163.

85

200.

64

OH

O

N

Me

OH

O

N

Me

67

1H and 13C NMR spectra of compound 2c

-101234567891011121314f1 (ppm)

3.00

1.08

1.00

1.07

1.09

0.95

1.03

1.02

0.85

2.47

6.87

6.87

6.89

6.90

6.90

6.92

6.92

7.03

7.03

7.06

7.06

7.31

7.32

7.32

7.32

7.33

7.33

7.34

7.34

7.47

7.48

7.49

7.50

7.50

7.52

7.53

7.76

7.76

7.77

8.08

8.08

8.10

8.11

8.56

8.58

12.5

3

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

21.3

8

118.

6111

8.98

119.

6712

5.53

127.

2013

4.41

136.

68

148.

0214

9.21

155.

1716

3.26

197.

46

OH

ON

Me

OH

ON

Me

68

1H and 13C NMR spectra of compound 2d

-101234567891011121314f1 (ppm)

3.02

1.00

0.93

1.01

1.00

0.96

0.96

0.92

0.83

2.45

6.87

6.87

6.89

6.90

6.92

6.92

7.03

7.03

7.03

7.05

7.06

7.06

7.46

7.47

7.49

7.49

7.50

7.70

7.70

7.70

7.71

7.72

7.72

7.73

7.73

7.86

7.89

8.16

8.16

8.18

8.19

8.54

8.54

8.54

8.54

12.5

1

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

18.8

1

118.

5611

8.91

119.

6212

4.58

134.

4213

6.54

137.

97

148.

6615

2.79

163.

29

196.

93

OH

ON

Me

OH

ON

Me

69

1H and 13C NMR spectra of compound 2e

-101234567891011121314f1 (ppm)

3.00

1.09

1.03

1.09

1.07

1.03

1.03

0.96

0.95

6.88

6.91

6.93

7.02

7.05

7.34

7.34

7.36

7.37

7.46

7.49

7.51

8.01

8.04

8.30

8.32

8.38

8.39

12.4

6

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

55.9

9

118.

4211

8.83

119.

5012

0.64

126.

6613

4.54

136.

3313

6.38

147.

81

157.

8316

3.34

195.

79

OH

ON

OMe

OH

ON

OMe

70

1H and 13C NMR spectra of compound 2f

-101234567891011121314f1 (ppm)

3.00

1.16

1.06

1.14

2.33

1.19

1.08

0.91

3.97

6.86

6.86

6.88

6.89

6.91

6.91

6.95

6.95

6.97

6.98

7.04

7.04

7.07

7.07

7.48

7.49

7.49

7.51

7.51

7.52

7.53

7.74

7.77

7.77

7.80

8.26

8.26

8.28

8.29

12.2

4

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

53.9

7

114.

3911

7.95

118.

4311

8.63

118.

94

134.

4313

6.68

139.

52

152.

82

162.

9516

4.00

197.

47

OH

ON OMe

OH

ON OMe

71

1H and 13C NMR spectra of compound 2g

-101234567891011121314f1 (ppm)

1.09

1.02

1.07

1.07

1.04

1.01

1.00

0.98

6.89

6.92

6.94

7.04

7.07

7.50

7.52

7.55

7.59

7.60

7.62

7.63

7.64

7.65

8.00

8.02

8.03

8.05

8.16

8.16

8.19

8.58

8.58

12.1

2

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

118.

5111

8.64

119.

0012

4.06

124.

3012

6.75

126.

8213

4.46

136.

8613

6.97

137.

1815

1.70

158.

9516

2.44

163.

92

195.

96

OH

ON

F

OH

ON

F

72

19F NMR spectra of compound 2g

-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10010f1 (ppm)

-120

.47

-120

.46

-120

.45

-120

.44

1H and 13C NMR spectra of compound 2h

-101234567891011121314f1 (ppm)

1.00

0.95

1.04

1.93

0.95

0.87

0.82

6.89

6.91

6.94

7.05

7.07

7.50

7.53

7.56

7.91

8.13

8.16

8.69

12.0

9

OH

ON

Cl

OH

ON

F

73

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

118.

5411

9.04

125.

7613

4.34

135.

1713

7.11

137.

2614

7.48

153.

34

163.

94

196.

31

1H and 13C NMR spectra of compound 2i

-101234567891011121314f1 (ppm)

1.14

1.11

1.12

1.05

1.04

1.11

1.00

1.00

6.88

6.88

6.90

6.90

6.91

6.93

6.93

7.04

7.04

7.07

7.07

7.49

7.50

7.52

7.52

7.53

7.55

7.55

7.82

7.82

7.85

7.85

8.04

8.04

8.06

8.07

8.12

8.12

8.15

8.15

8.78

8.79

8.79

8.79

12.0

7

OH

ON

Cl

OH

ON

Br

74

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

118.

5711

8.60

119.

0512

4.26

126.

0513

4.33

137.

1214

0.19

149.

6815

3.75

163.

98

196.

45

1H and 13C NMR spectra of compound 2j

-101234567891011121314f1 (ppm)

1.12

1.03

1.12

2.05

1.08

1.00

1.00

6.89

6.89

6.89

6.91

6.92

6.92

6.94

6.94

6.94

7.06

7.07

7.07

7.09

7.09

7.10

7.52

7.53

7.55

7.55

7.56

7.57

7.58

8.01

8.01

8.02

8.03

8.04

8.04

8.05

8.06

8.16

8.16

8.17

8.19

8.19

8.19

9.00

9.00

9.01

9.01

11.9

7

OH

ON

CF3

OH

ON

Br

75

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

118.

4211

8.72

119.

2212

1.84

124.

3912

4.55

128.

4112

8.75

134.

3013

4.79

134.

8213

4.86

134.

8913

7.53

145.

5514

5.59

145.

6314

5.67

158.

4616

4.22

196.

49

19F NMR spectra of compound 2j

-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10010f1 (ppm)

-62.

59

OH

ON

CF3

OH

ON

CF3

76

1H and 13C NMR spectra of compound 2k

-101234567891011121314f1 (ppm)

2.07

3.16

0.98

1.01

1.00

0.81

7.00

7.01

7.03

7.03

7.04

7.05

7.05

7.06

7.06

7.07

7.08

7.52

7.52

7.54

7.55

7.57

7.57

7.58

7.59

7.60

7.62

7.62

7.99

7.99

7.99

8.01

8.02

8.02

8.23

8.23

8.23

8.23

8.25

8.26

9.24

9.24

9.26

9.27

12.1

0

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

118.

2811

8.57

119.

7012

2.26

125.

8512

7.28

128.

0113

4.22

136.

8613

7.69

153.

81

164.

3116

7.24

187.

79

O

S

N

OH

O

S

N

OH

77

1H and 13C NMR spectra of compound 2l

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.513.5f1 (ppm)

3.00

2.94

0.97

0.92

0.89

0.98

0.87

0.81

2.55

2.60

6.83

6.83

6.85

6.85

6.86

6.88

6.88

7.06

7.07

7.09

7.10

7.27

7.28

7.29

7.31

7.31

7.51

7.52

7.54

7.54

7.55

8.52

11.9

3

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

21.1

721

.23

118.

7411

8.92

119.

34

133.

4813

7.69

144.

9614

8.61

148.

8115

0.10

164.

07

199.

40

OH

O

N

N Me

Me

OH

O

N

N Me

Me

78

1H and 13C NMR spectra of compound 2m

-101234567891011121314f1 (ppm)

3.00

1.00

0.94

1.02

2.04

0.98

0.98

0.87

2.37

6.70

6.73

6.86

7.91

7.92

7.98

8.01

8.72

8.73

12.3

8

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

22.2

0

116.

8211

8.55

120.

4112

4.62

126.

0813

4.27

137.

47

148.

4014

8.65

155.

6216

3.87

196.

87

OH

ON

Me

OH

ON

Me

79

1H and 13C NMR spectra of compound 2n

-101234567891011121314f1 (ppm)

3.14

1.08

1.05

1.03

3.09

1.00

0.92

2.31

6.77

6.80

6.83

7.37

7.39

7.46

7.46

7.47

7.47

7.48

7.48

7.49

7.49

7.50

7.50

7.51

7.88

7.88

7.89

7.90

7.91

8.71

8.72

8.73

8.73

12.5

3

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

15.8

5

118.

2311

8.33

124.

5512

6.01

127.

3913

2.03

137.

3713

7.63

148.

5015

5.71

162.

23

198.

08

OH

ON

Me

OH

ON

Me

80

1H and 13C NMR spectra of compound 2o

-101234567891011121314f1 (ppm)

3.00

0.96

0.99

0.91

0.93

1.83

0.88

0.81

3.94

6.83

6.86

6.88

7.09

7.12

7.53

7.54

7.55

7.67

7.67

7.70

7.70

7.94

7.94

7.96

7.97

8.72

8.74

12.7

8

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

56.4

4

117.

3211

8.38

119.

8512

4.82

125.

4512

6.42

137.

74

148.

2214

9.24

153.

6915

5.34

197.

32

OH

ON

OMe

OH

ON

OMe

81

1H and 13C NMR spectra of compound 2p

-101234567891011121314f1 (ppm)

1.00

2.03

2.09

0.96

0.97

0.79

6.94

6.97

7.55

7.55

7.56

7.58

7.58

7.58

7.59

7.96

7.96

7.98

7.99

8.00

8.01

8.01

8.01

8.37

8.38

8.74

8.74

12.6

3

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

110.

7312

0.78

121.

0512

5.12

126.

8613

6.39

138.

0113

9.27

148.

1615

4.59

162.

10

195.

26

OH

ONBr

OH

ONBr

82

1H and 13C NMR spectra of compound 2q

-101234567891011121314f1 (ppm)

1.06

1.16

1.04

1.15

2.01

1.00

0.88

6.99

7.01

7.02

7.04

7.22

7.23

7.24

7.25

7.25

7.26

7.27

7.27

7.29

7.53

7.53

7.54

7.55

7.55

7.55

7.57

7.57

7.93

7.93

7.95

7.96

7.98

7.98

8.00

8.01

8.01

8.04

8.05

8.73

8.75

12.3

3

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

119.

0511

9.18

119.

3811

9.80

119.

8912

4.20

124.

5112

5.03

126.

7513

7.87

148.

1915

3.29

154.

7815

6.43

159.

63

195.

47

OH

ONF

OH

ONF

83

19F NMR spectra of compound 2q

-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10010f1 (ppm)

-124

.33

-124

.32

-124

.31

-124

.30

-124

.30

-124

.29

-124

.28

1H and 13C NMR spectra of compound 2r

-101234567891011121314f1 (ppm)

1.01

1.01

1.04

2.08

0.95

1.00

0.87

7.00

7.03

7.43

7.43

7.45

7.46

7.54

7.54

7.56

7.56

7.57

7.58

7.58

7.94

7.94

7.96

7.96

7.97

7.99

7.99

8.01

8.01

8.01

8.03

8.23

8.24

8.74

8.75

12.6

0

OH

ONCl

OH

ONF

84

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

120.

2912

0.34

123.

7012

5.10

126.

8513

3.37

136.

5313

7.99

148.

1715

4.58

161.

70

195.

42

1H and 13C NMR spectra of compound 2s

-1.00.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.513.5f1 (ppm)

3.00

3.08

1.09

2.13

1.04

1.03

1.00

0.84

2.30

3.93

6.78

6.80

6.83

7.31

7.32

7.34

7.35

7.37

7.96

7.99

8.08

8.08

8.10

8.11

8.37

8.38

12.6

3

OH

ONCl

OH

ON

OMeMe

85

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

15.9

0

55.9

3

118.

1211

8.48

120.

4312

6.46

127.

1713

2.12

136.

5013

7.15

148.

08

157.

6216

2.02

196.

54

1H and 13C NMR spectra of compound 2t

-1.00.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.513.5f1 (ppm)

3.03

3.00

1.03

0.99

1.00

0.96

0.96

0.94

0.75

2.31

2.44

6.77

6.80

6.82

7.35

7.38

7.68

7.70

7.70

7.71

7.71

7.71

7.81

7.83

7.93

7.94

7.94

7.94

7.96

7.96

7.97

7.97

8.54

8.54

8.54

8.55

12.6

3

OH

ON

MeMe

OH

ON

OMeMe

86

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

15.8

918

.79

118.

2411

8.48

124.

3912

7.30

132.

0313

6.51

137.

4013

7.72

148.

8615

3.07

162.

04

197.

81

1H and 13C NMR spectra of compound 2u

-101234567891011121314f1 (ppm)

3.00

3.00

1.01

0.95

0.96

0.95

0.96

0.96

0.78

2.31

2.46

6.77

6.79

6.82

7.29

7.29

7.29

7.30

7.30

7.31

7.36

7.36

7.38

7.70

7.70

7.71

7.86

7.86

7.87

7.89

7.89

8.56

8.57

12.6

2

OH

ON

MeMe

OH

ON

MeMe

87

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

15.8

821

.33

118.

3111

8.53

125.

3412

6.93

127.

3613

2.03

137.

52

148.

2114

8.90

155.

5416

2.03

198.

31

1H and 13C NMR spectra of compound 2v

-101234567891011121314f1 (ppm)

3.00

3.05

1.04

1.05

1.03

1.07

1.07

0.99

0.91

3.93

3.96

6.83

6.86

6.88

7.08

7.10

7.28

7.35

7.36

7.38

7.39

7.85

7.86

7.88

7.89

8.03

8.06

8.37

8.38

12.8

3

OH

ON

MeMe

OH

ON

OMeOMe

88

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

56.0

356

.38

116.

9111

8.14

120.

1012

0.77

125.

5812

6.72

136.

24

147.

8014

9.13

153.

4815

7.93

195.

78

1H and 13C NMR spectra of compound 2w

-101234567891011121314f1 (ppm)

3.00

0.99

1.12

1.02

1.00

0.97

0.97

0.82

2.47

6.98

6.99

7.01

7.02

7.20

7.21

7.23

7.23

7.23

7.24

7.24

7.26

7.27

7.73

7.74

7.74

7.76

7.76

7.76

7.76

7.95

7.97

8.05

8.06

8.08

8.09

8.55

8.55

8.55

12.5

2

OH

ON

OMeOMe

OH

ONF

Me

89

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

18.8

7

119.

0511

9.38

119.

5111

9.60

119.

8111

9.91

123.

9512

4.27

124.

8913

7.51

138.

3014

8.50

152.

2115

3.34

156.

4815

9.35

195.

05

19F NMR spectra of compound 2w

-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10010f1 (ppm)

-124

.57

-124

.55

-124

.55

-124

.54

-124

.53

-124

.53

-124

.52

OH

ONF

Me

OH

ONF

Me

90

1H and 13C NMR spectra of compound 2z

-101234567891011121314f1 (ppm)

1.00

0.93

0.97

1.02

1.94

1.90

0.90

6.88

6.88

6.90

6.90

6.91

6.93

6.93

7.09

7.09

7.12

7.12

7.44

7.44

7.46

7.47

7.53

7.54

7.56

7.56

7.57

7.58

7.59

7.75

7.75

7.75

7.76

7.77

7.78

7.81

7.82

7.83

7.84

7.84

11.7

9

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

115.

3311

7.86

118.

4911

8.79

119.

0612

9.43

132.

2013

3.02

137.

2114

1.55

163.

41

199.

72

OH

O

CN

OH

O

CN

91

1H and 13C NMR spectra of compound 2aa

-101234567891011121314f1 (ppm)

3.00

1.09

0.99

2.15

2.04

2.05

0.92

3.98

6.89

6.89

7.08

7.08

7.08

7.10

7.10

7.10

7.11

7.50

7.50

7.50

7.51

7.53

7.53

7.53

7.71

7.72

7.72

7.74

7.74

7.74

8.16

8.16

8.17

8.18

8.19

8.19

11.9

3

-100102030405060708090100110120130140150160170180190200210220230f1 (ppm)

52.6

9

118.

7611

9.05

129.

0912

9.73

133.

0313

3.53

137.

0114

1.79

163.

5016

6.35

167.

04

201.

09

OH

O

CO2Me

OH

O

CO2Me

92

1H and 13C NMR spectra of compound 2ab

-101234567891011121314f1 (ppm)

1.00

0.96

2.00

3.77

0.84

6.87

6.88

6.90

6.90

6.90

6.92

6.93

7.09

7.09

7.12

7.12

7.49

7.49

7.52

7.52

7.53

7.53

7.55

7.55

7.56

7.58

7.58

7.79

11.8

9

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

118.

8811

8.94

119.

1512

2.43

124.

5512

5.14

125.

5812

5.61

125.

6512

5.69

129.

4713

3.42

133.

4713

3.75

137.

1814

1.21

163.

59

200.

60

OH

O

CF3

OH

O

CF3

93

1H and 13C NMR spectra of compound 2ac

-1.00.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.5f1 (ppm)

1.00

0.93

1.00

1.02

3.95

0.81

6.84

6.85

6.87

6.87

6.88

6.90

6.90

7.05

7.05

7.08

7.08

7.17

7.18

7.20

7.21

7.21

7.23

7.24

7.27

7.27

7.29

7.30

7.32

7.32

7.40

7.41

7.41

7.41

7.43

7.43

7.44

7.44

7.45

7.45

7.47

7.48

7.50

7.50

7.51

7.52

7.53

7.53

7.54

7.54

7.54

7.55

7.55

7.55

7.56

7.56

7.57

7.58

7.59

11.9

8

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

116.

3911

6.60

118.

4811

9.24

119.

9012

4.54

124.

5712

6.41

126.

5613

0.05

130.

0713

3.04

133.

1213

3.56

133.

5813

7.25

158.

0116

0.51

163.

20

198.

74

OH

O F

OH

O F

94

19F NMR spectra of compound 2ac

-210-200-190-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-10010f1 (ppm)

-112

.31

-112

.31

-112

.30

-112

.30

-112

.29

-112

.29

-112

.28

-112

.28

-112

.26

-112

.26

-112

.25

1H and 13C NMR spectra of compound 2ad

-3-2-1012345678910111213141516f1 (ppm)

1.00

0.95

1.86

1.97

0.86

0.85

6.82

6.82

6.84

6.84

6.84

6.86

6.86

7.06

7.06

7.08

7.08

7.21

7.21

7.22

7.23

7.23

7.24

7.51

7.51

7.52

7.53

7.53

7.53

7.54

7.55

7.56

7.67

7.68

11.8

3

OH

O F

O

OH

Br

Cl

95

0102030405060708090100110120130140150160170180190200210f1 (ppm)

118.

7011

9.34

119.

4212

4.81

129.

8713

0.29

132.

2013

3.01

133.

4213

6.38

137.

64

163.

44

199.

68

1H and 13C NMR spectra of compound 2ae

-2-101234567891011121314f1 (ppm)

6.00

1.00

2.87

0.96

1.14

0.98

0.78

2.16

6.76

6.77

6.79

6.79

6.81

6.82

7.05

7.05

7.05

7.08

7.08

7.08

7.11

7.15

7.15

7.18

7.18

7.24

7.26

7.26

7.26

7.27

7.29

7.47

7.48

7.49

7.50

7.50

7.52

7.53

12.3

2

O Me

Me

OH

O

OH

Br

Cl

96

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

19.5

3

118.

5111

9.54

120.

2312

7.78

129.

3313

2.82

134.

1513

7.23

138.

27

163.

10

206.

61

1H and 13C NMR spectra of compound 2af

-101234567891011121314f1 (ppm)

3.00

1.06

3.13

2.02

2.12

0.82

3.78

6.78

6.78

6.81

6.83

6.83

7.01

7.02

7.03

7.04

7.05

7.06

7.09

7.28

7.29

7.31

7.31

7.33

7.33

7.35

7.36

7.45

7.46

7.46

7.47

7.48

7.49

7.50

7.51

7.51

12.2

0

O Me

Me

OH

OH

O OMe

97

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

55.8

3

111.

5611

8.23

118.

8812

0.33

120.

6612

7.88

129.

0013

2.03

133.

9513

6.68

156.

68

163.

05

202.

31

1H and 13C NMR spectra of compound 2ag

-101234567891011121314f1 (ppm)

6.00

1.96

0.99

0.93

0.92

1.01

0.98

0.74

3.73

6.62

6.65

6.76

6.76

6.79

6.81

6.81

7.01

7.01

7.03

7.04

7.27

7.27

7.30

7.30

7.35

7.38

7.41

7.43

7.44

7.46

7.47

7.48

7.49

12.1

6

O OMe

MeO

OH

OH

O OMe

98

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

56.0

9

104.

12

116.

5511

8.05

119.

0712

1.14

131.

4913

3.21

136.

58

157.

4616

2.70

201.

49

O OMe

MeO

OH