ElectronicSupplementaryInformationS10 7.Characterizationforalltheproducts....

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Electronic Supplementary Information

for

Visible-light-induced denitrogenative phosphorylation ofbenzotriazinones: a metal- and additive-free method foraccessing ortho-phosphorylated benzamide derivatives

Fushan Chen, Shanshan Hu, Sipei Li, Guo Tang,* and Yufen Zhao

Department of Chemistry, College of Chemistry and Chemical Engineering, and the KeyLaboratory for Chemical Biology of Fujian Province, Xiamen University, Xiamen, Fujian361005, ChinaE-mail: [email protected]

Table of Contents

1. General information......................................................................................................... S22. General preparation of 1,2,3-Benzotriazin-4(3H)-one derivatives............................... S23. General procedure for photo-reaction………………………….................................... S44. Investigation for reaction mechanism…………………………………………………. S55. Luminescence quenching experiments............................................................................ S66. Cyclic voltammetry studies……………………………………………………………. S97. Characterization for all the products………………..................................................... S108. 1H, 13C and 31PNMR spectrum for all the products……............................................. S27

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

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1. General information.All reactions were carried out under dry argon. all reagents and solvents were obtained fromcommercial suppliers and used without further purification. 1H, 13C and 31P NMR spectra weremeasured on Bruker AV 500M spectrometers with CDCl3 as solvent and tetramethylsilane (TMS)as internal standard for 1H and 13C NMR spectra, 85% H3PO4 as external standard for 31P NMRspectra. Data are represented as follows: chemical shift, multiplicity (s = singlet, d = doublet, t =triplet, q = quartet, m = multiplet, dd = doublet of doublets, dt = doublet of triplets), couplingconstants in Hertz (Hz). The products were purified by column chromatography on silica gel300-400 mesh. The unknown products were further characterized by HRMS (FT-ICR-MS) and anelectrospray ionization source in positive-ion mode.

2. General preparation of 1,2,3-Benzotriazin-4(3H)-one derivatives.

Method A: (1a-1c, 1f-1m, 1o-1q, 1s).1

A mixture of the benzo[d][1,2,3]triazin-4(3H)-one (5.0 mmol), organoboronic acid (7.5 mmol),anhydrous Cu(OAc)2 (5.0 mmol) and Et3N (10.0 mmol) in DCE (30.0 mL) was stirred at roomtemperature till the reaction finished (monitored by TLC). The reaction mixture was filteredthrough celite. The filtrate was collected, concentrated in vacuo, and the residue was purified bychromatography on silica gel using hexane/ethyl acetate to afford the desired product.

Method B: (1d-1e, 1n, 1r, 1t, 1x).2

To a round bottom flask containing methyl anthranilate derivatives (10.0 mmol) were evacuatedand purged with argon three times. and then HCl(aq) (16.0 mL, 2 M) was added, then stirred at0 °C for 5 min. A solution of NaNO2 (11.7 mmol) in water (5.5 mL) were slowly added within 40min to the system and then stirred at 0 °C for 30 min. Then, a solution of NaOAc (38.6 mmol) inwater (12.5 mL) was slowly added within 20 min, followed by addition of corresponding anilines(15.2 mmol) at 0 °C. The resulting mixture was stirred at 0 °C for 3 h. The precipitate wascollected by filtration, washed with cold water (25.0 ml). The above triazene and morpholine (30.0mmol) was refluxed in ethanol (75.0 mL) until triazene was completely consumed. The reactionmixture was cooled to -30 °C for crystallization. The product was collected by filtration andwashed with cold ethanol to give corresponding products as white solid.

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Method C: (1u-1w, 1y,)3,4

To a stirred solution of anthranilic acid derivatives (10.0 mmol) in dichloromethane (CH2Cl2)(30.0 mL) was added EDCl·HCl (12.0 mmol), HOBt (12.0 mmol) and aniline derivatives (12.0mmol) followed by the dropwise addition of DIPEA (25.0 mmol). The reaction mixture wasallowed to stir at room temperature until the completion of reaction was monitored by TLC (24 ~36 h). After completion, the reaction mixture was diluted with ice water (90.0 mL) followed by theextraction with ethyl acetate (3*60 mL). The combined organic layer was washed with 1M HC1(100.0 mL) followed by saturated brine solution, dried over Na2SO4 and concentrated undervacuum. The obtained crude purified by silica gel column chromatograph using petroleumether/ethyl acetate as the eluent to afford the desired products.To a stirred solution of 2-amino-N-phenylbenzamide derivative (8 mmol) in MeCN (50.0 mL)

were added NaNO2 (24. 0 mmol) and I2 (8.0 mmol) at room temperature and the mixture was thenheated at 80 °C for 3 h. then the solvent was removed under vacuum and the residue was dilutedwith H2O (200 mL) and extracted with EtOAc (3x80 mL). The combined organic layer was driedover Na2SO4 and evaporated under reduced pressure. The crude residue was purified by columnchromatography over silica gel using petroleum ether/ethyl acetate (4:1, v/v) as the eluent toafford the desired product.

Method D: (1z).4

A schlenk tube containing 1,2,3-benzotriazin-4(3H)-one (10.0 mmol), K2CO3 (14.7 mmol) wereevacuated and purged with argon three times. Dry DMF (14.7 mL), alkyl bromide (16.2 mmol)were sequentially added to the system at 0 °C. Subsequently, the mixture was stirred at roomtemperature for 12 h, and then quenched with addition of water (120.0 mL), extracted with ethylacetate (3*80 mL). The combined organic layer were washed with brine and dried over MgSO4.The solvent was removed under reduced pressure and the residue was purified by flashchromatography using petroleum ether/ethyl acetate as the eluent to afford the desired products.1. K. S. Kumar, R. Adepua, S. Sandraa, D. Rambabua, G. R. Krishna, C. M. Reddy, P. Misraa andM. Pal, Bioorg. Med. Chem. Lett., 2012, 22, 1146-1150.2. a) Y. Motoshi, M. Masao, M. Tomoya and M. Masahiro, J. Am. Chem. Soc., 2010, 132, 54- 55;b) A. S. Clark, B. Deans, M. F. G. Stevens, M. J. Tisdale, R. T. Wheelhouse, B. J. Denny and J. A.Hartley, J. Med. Chem., 1995, 38, 1493-1504; c) V. H. Thorat, N. S. Upadhyay, M. Murakami andC. –H. Cheng, Adv. Synth. Catal., 2018, 360, 284-289.3. a) G. C. Senadi, V. S. Kudale and J.-J. Wang, Green Chem., 2019, 21, 979-985; b) D. S. Barak,S. Mukhopadhyay, D. J. Dahatonde and S. Batra, Tetrahedron Lett., 2019, 60, 248-251.4. T. Miura, M. Yamauchi and M. Murakami, Org. Lett., 2008, 10, 3085-3088.

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3. General procedure for photoreaction.

Organic-dye-catalyzed denitrogenative phosphorylation of benzotriazinones

A schlenk tube containing benzotriazinone derivatives (1, 0.2 mmol) and eosin Y (0.01 mmol)were evacuated and purged with argon three times. DIPEA (0.4 mmol), phosphorylation reagent (2,0.3 mmol), H2O (0.3 mL) and CH3CN (2.0 mL) were sequentially added to the system at roomtemperature. Then the system stirred at room temperature under the irradiation of 30 W blue LEDsfor 90 min (or irradiated by sunlight at 25-30 oC for 6 h). Afterwards, the solvent was removed invacuum, and residues were purified by silica gel column chromatograph using petroleumether/ethyl acetate as the eluent (2:1) to afford the desired phosphorylation products.

Gram-scale preparation of 3a and 4i

A round flask containing benzotriazinone derivatives 1a, and eosin Y (5 mol %) were evacuatedand purged with argon three times. DIPEA (2.0 equiv), phosphorylation reagent 2a (2g) (1.5 equiv)A mixture of H2O and CH3CN (0.3:2.0) were sequentially added to the system at roomtemperature. Then the system stirred at room temperature under the irradiation of 30 W blue LEDsfor 24 hours (or irradiated by sunlight at 25-30 oC for 36 h). Quenched with addition of potassiumcarbonate and water (6 mL/1 mmol) to pH = 8.5 and extracted with ethyl acetate (3*60 mL). Thecombined organic layer were removed in vacuum, dried over with MgSO4. Recrystallization usinga petroleum ether/AcOEt mixture as the solvent to afford the desired phosphorylation products.

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4. Investigation for reaction mechanism.

A schlenk tube containing benzotriazinone derivative (1a, 0.2 mmol), eosin Y (0.01 mmol) andTEMPO (1.0 mmol) were evacuated and purged with argon three times. DIPEA (0.4 mmol),phosphorylation reagent (2a, 0.3 mmol), H2O (0.3 mL) and CH3CN (2.0 mL) were sequentiallyadded to the system at room temperature. Then the system stirred at room temperature under theirradiation of 30 W blue LEDs for 90 min.

A schlenk tube containing benzotriazinone derivatives (1, 0.2 mmol), B2pin2 (4, 0.4 mmol) andeosin Y (0.01 mmol) were evacuated and purged with argon three times. DIPEA (0.4 mmol), H2O(0.3 mL) and CH3CN (2.0 mL) were sequentially added to the system at room temperature. thenthe system stirred at room temperature under the irradiation of 30 W blue LEDs for 90 min.Remove the solvent under vacuum, residues were purified by silica gel column chromatographusing petroleum ether/ethyl acetate as the eluent (4:1) to afford the desired products.

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5. Luminescence quenching experiments.

the emission spectra of a 4.3 × 10-3 M solution of eosin Y in degassed CH3CN: H2O = 20:3 excitedat 575 nm;

the emission spectra of a 4.3 × 10-3 M solution of eosin Y with various concentrations of DIPEA inin degassed CH3CN: H2O = 20:3 excited at 575 nm;

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The Stern−Volmer plot of a 4.3 × 10-3 M solution of eosin Y with various concentrations ofDIPEA in in degassed CH3CN: H2O = 20:3 excited at 575 nm;

the emission spectra of a 4.3 × 10-3 M solution of eosin Y with various concentrations of 1a indegassed anhydrous CH3CN: H2O = 20:3 excited at 575 nm;

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the emission spectra of a 4.3 × 10-3 M solution of eosin Y with various concentrations of 2a indegassed anhydrous CH3CN: H2O = 20:3 excited at 575 nm.

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6. Cyclic Voltammetry StudiesThe cyclic voltammograms were recorded in an electrolyte of Et4NPF6 (0.1 M) in the indicatedsolvent (6 mL) using a glassy carbon disk working electrode (diameter, 1 mm), a Pt wire auxiliaryelectrode and a SCE reference electrode. The scan rate was 100 mV/s.

Cyclic voltammogram of DIPEA (10 mM) in MeCN, Ep/2ox = 0.63 V.

Cyclic voltammogram of 1a (10 mM) in MeCN, Ep/2ox = 2.04 V

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7. Characterization for all the products.

Diethyl (2-(phenylcarbamoyl)phenyl)phosphonate (3a, CAS NO. 41327-48-4)

White solid; 60.6 mg, 91% yield; 1H NMR (CDCl3, 500 MHz): δ 9.15 (s, 1H), 7.91-7.86 (m, 2H),

7.72 (d, J = 7.6 Hz, 2H), 7.64 (t, J = 7.7 Hz, 1H), 7.56-7.53 (m, 1H), 7.34 (t, J = 8.0 Hz, 2H), 7.12

(t, J = 7.2 Hz, 1H), 4.17-4.12 (m, 4H), 1.28 (t, J = 7.3 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz):

δ 166.5 (d, J = 4.5 Hz), 140.4 (d, J = 10.0 Hz), 138.5, 133.0 (d, J = 2.2 Hz), 132.8 (d, J = 8.9 Hz),

130.8 (d, J = 13.2 Hz), 130.3 (d, J = 13.8 Hz), 129.2, 125.2 (d, J = 187.0 Hz), 124.7, 120.2, 63.5

(d, J = 6.7 Hz), 16.4 (d, J = 6.7 Hz); 31P NMR (CDCl3, 202 MHz): δ 17.78; IR (film) υmax: 2979,

1605, 1679, 1601, 1543, 1441, 1322, 1230, 1142, 1104, 988, 755 cm-1; HRMS: [M+H]+ m/z calcd

for C17H21NO4P+ 334.1203, found 334.1205.

Diethyl (2-(m-tolylcarbamoyl)phenyl)phosphonate (3b, new compound)


7.64 (d, J = 7.4 Hz, 1H), 7.55-7.51 (m, 3H), 7.23 (t, J = 7.7 Hz, 1H), 6.94 (d, J = 7.5 Hz, 1H),

4.17-4.13 (m, 4H), 2.35 (s, 3H), 1.29 (t, J = 7.1 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ

166.4 (d, J = 5.5 Hz), 140.5 (d, J = 10.9 Hz), 139.1, 138.4, 133.0 (d, J = 2.6 Hz), 132.7 (d, J = 8.3

Hz), 130.8 (d, J = 13.2 Hz), 130.2 (d, J = 14.3 Hz), 129.0, 125.5, 125.2 (d, J = 187.1 Hz), 120.7,

117.2, 63.4 (d, J = 6.6 Hz), 21.7, 16.4 (d, J = 6.6 Hz); 31P NMR (CDCl3, 202 MHz): δ 17.87; IR

(film) υmax: 3265, 2982, 1680, 1614, 1511, 1489, 1372, 1025, 970, 780, cm-1; HRMS: [M+H]+

m/z calcd for C18H23NO4P+ 348.1359, found 348.1358.

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Diethyl (2-(o-tolylcarbamoyl)phenyl)phosphonate (3c, new compound)

White solid; 59.0 mg, 85% yield; 1H NMR (CDCl3, 500 MHz): δ 8.52 (s, 1H), 8.02 (d, J = 8.7 Hz,

1H), 7.92 (dd, J1 = 14.2 Hz, J2 = 7.6 Hz, 1H), 7.82 (t, J = 6.2 Hz, 1H), 7.64 (t, J = 7.6 Hz, 1H),

7.57-7.54 (m, 1H), 7.24 (t, J = 7.9 Hz, 1H), 7.20 (d, J = 7.5 Hz, 1H), 7.09 (t, J = 7.4 Hz, 1H),


166.8 (d, J = 4.4 Hz), 140.6 (d, J = 9.9 Hz), 136.1, 132.97 (d, J = 3.3 Hz), 132.96 (d, J = 7.7 Hz),

130.7, 130.20 (d, J = 13.2 Hz), 130.17, 130.0 (d, J = 13.6 Hz), 126.8, 125.5, 125.4 (d, J = 187.1

Hz), 123.1, 63.3 (d, J = 5.5 Hz), 18.0, 16.4 (d, J = 6.6 Hz); 31P NMR (CDCl3, 202 MHz): δ 17.57;

IR (film) υmax: 2983, 1679, 1532, 1488, 1453, 1312, 1024, 981, 752 cm-1; HRMS: [M+Na]+ m/z

calcd for C18H22NO4PNa+ 370.1179, found 370.1179.

Diethyl (2-((2-bromophenyl)carbamoyl)phenyl)phosphonate (3d, CAS NO.: 126391-00-6)

White solid; 67.4 mg, 82% yield; 1H NMR (CDCl3, 500 MHz): δ 8.43 (d, J = 7.9 Hz, 1H), 8.35 (s,

1H), 8.00 (dd, J1 = 14.2 Hz, J2 = 7.6 Hz, 1H), 7.71 (t, J = 6.7 Hz, 1H), 7.64 (t, J = 7.6 Hz, 1H),

7.57-7.55 (m, 2H), 7.36 (t, J = 7.4 Hz, 1H), 7.01 (d, J = 8.0 Hz, 1H), 4.17-4.11 (m, 4H), 1.28 (t, J

= 6.8 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 167.1 (d, J = 5.5 Hz), 140.3 (d, J = 9.9 Hz),

136.0, 133.7 (d, J = 8.9 Hz), 132.9 (d, J = 3.3 Hz), 132.7, 130.3 (d, J = 13.5 Hz), 129.1 (d, J =

13.4 Hz), 128.5, 126.0 (d, J = 187.2 Hz), 125.9, 122.8, 114.4, 63.1 (d, J = 6.6 Hz), 16.5 (d, J = 6.6

Hz); 31P NMR (CDCl3, 202 MHz): δ 16.28; IR (film) υmax: 2959, 1665, 1588, 1537, 1483, 1432,

1318, 1223, 1167, 1054, 1012, 965, 753 cm-1; HRMS: [M+Na]+ m/z calcd for C17H19BrNO4PNa+

434.0127, found 434.0127.

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Diethyl (2-((2-iodophenyl)carbamoyl)phenyl)phosphonate (3e, new compound)


1H), 8.01 (dd, J1 = 14.0 Hz, J2 = 7.1 Hz, 1H), 7.81 (dd, J1 = 8.1 Hz, J2 = 1.1 Hz, 1H), 7.75-7.73 (m,

1H), 7.65 (t, J = 7.4 Hz, 1H), 7.59-7.56 (m, 1H), 7.40 (t, J = 7.7 Hz, 1H), 6.91-6.88 (m, 1H),

4.19-4.12 (m, 4H), 1.30 (t, J = 7.1 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 167.1 (d, J = 4.4

Hz), 140.3 (d, J = 9.6 Hz), 139.2, 138.6, 133.8 (d, J = 8.8 Hz), 132.9 (d, J = 3.3 Hz), 130.3 (d, J =

14.3 Hz), 129.4, 129.0 (d, J = 13.3 Hz), 128.8, 126.1 (d, J = 187.2 Hz), 123.3, 91.1, 63.2 (d, J =

6.6 Hz), 16.5 (d, J = 6.6 Hz); 31P NMR (CDCl3, 202 MHz): δ 16.85; IR (film) υmax: 2981, 1682,

1583, 1517, 1431, 1300, 1246, 1142, 1019, 970, 753, 1180, 1142, 1075, 960, 752 cm-1; HRMS:

[M+Na]+ m/z calcd for C17H19INO4PNa+ 481.9989, found 481.9990.

Diethyl (2-((4-fluorophenyl)carbamoyl)phenyl)phosphonate (3f, new compound)


7.70-7.68 (m, 2H), 7.64-7.62 (m, 1H), 7.55-7.52 (m, 1H), 7.03-7.00 (m, 2H), 4.16-4.10 (m, 4H),

1.28 (t, J = 7.3 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 166.3 (d, J = 5.5 Hz), 159.6 (d, J =

243.2 Hz), 140.1 (d, J = 11.0 Hz), 134.4 (d, J = 2.2 Hz), 133.0 (d, J = 3.3 Hz), 132.6 (d, J = 8.8

Hz), 130.8 (d, J = 13.2 Hz), 130.3 (d, J = 13.3 Hz), 125.2 (d, J = 187.1 Hz), 121.9 (d, J = 7.7 Hz),

115.8 (d, J = 22.1 Hz), 63.5 (d, J = 6.6 Hz), 16.4 (d, J = 6.7 Hz); 31P NMR (CDCl3, 202 MHz): δ

17.80 (d, J = 11.4 Hz); IR (film) υmax: 3258, 3065, 2930, 1675, 1616, 1589, 1549, 1509, 1406,

1323, 1158, 1076, 1026, 972, 835, 791, 751 cm-1; HRMS: [M+Na]+ m/z calcd for

C17H19FNO4PNa+ 374.0928, found 374.0928.

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Diethyl (2-((4-chlorophenyl)carbamoyl)phenyl)phosphonate (3g, new compound)


7.69 (d, J = 8.8 Hz, 2H), 7.63 (t, J = 7.6 Hz, 1H), 7.55-7.52 (m, 1H), 7.29 (d, J = 8.7 Hz, 2H),

4.16-4.11 (m, 4H), 1.28 (t, J = 7.1 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 166.4 (d, J = 4.4

Hz), 140.0 (d, J = 11.0 Hz), 137.1, 133.0 (d, J = 3.3 Hz), 132.6 (d, J = 7.8 Hz), 130.9 (d, J = 13.2

Hz), 130.4 (d, J = 13.4 Hz), 129.5, 129.2, 125.2 (d, J = 187.3 Hz), 121.4, 63.5 (d, J = 5.5 Hz), 16.4

(d, J = 6.6 Hz); 31P NMR (CDCl3, 202 MHz): δ 17.80; IR (film) υmax: 2968, 1680, 1597, 1539,

1493, 1398, 1318, 1233, 1143, 1093, 1025, 970, 829, 652 cm-1; HRMS: [M+Na]+ m/z calcd for

C17H19ClNO4PNa+ 390.0632, found 390.0629.

Diethyl (2-((4-(trifluoromethyl)phenyl)carbamoyl)phenyl)phosphonate (3h, new compound)


7.64-7.62 (m, 1H), 7.57-7.52 (m, 3H), 4.16-4.10 (m, 4H), 1.29 (t, J = 7.0 Hz, 6H); 13C{1H} NMR

(CDCl3, 125 MHz): δ 166.7 (d, J = 5.4 Hz), 141.6, 139.8 (d, J = 11.0 Hz), 133.0 (d, J = 2.1 Hz),

132.6 (d, J = 8.7 Hz), 130.9 (d, J = 13.1 Hz), 130.5 (d, J = 14.5 Hz), 126.4 (q, J = 3.4 Hz), 126.2

(q, J = 33.2 Hz), 125.3 (d, J = 186.8Hz), 124.4 (q, J = 271.6 Hz), 119.8, 63.5 (d, J = 6.5 Hz), 16.4

(d, J = 6.6 Hz); 31P NMR (CDCl3, 202 MHz): δ 17.80 (d, J = 9.2 Hz); IR (film) υmax: 2980, 1682,

1606, 1543, 1409, 1323, 1230, 1113, 1066, 1025, 971, 843, 748 cm-1; HRMS: [M+Na]+ m/z calcd

for C18H19F3NO4PNa + 424.0896, found 424.0893.

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Methyl 4-(2-(diethoxyphosphoryl)benzamido)benzoate (3i, new compound)


2H), 7.89-7.80 (m, 4H), 7.64 (t, J = 7.8 Hz, 1H), 7.57-7.54 (m, 1H), 4.16-4.11 (m, 4H), 3.89 (s,

3H), 1.28 (t, J = 7.1 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 166.9, 166.6 (d, J = 5.5 Hz),

142.7, 139.9 (d, J = 10.7 Hz), 133.0 (d, J = 3.2 Hz), 132.6 (d, J = 7.7 Hz), 131.01, 130.96 (d, J =

9.9 Hz), 130.5 (d, J = 14.0 Hz), 125.9, 125.3 (d, J = 187.1 Hz), 119.3, 63.5 (d, J = 6.6 Hz), 52.2,

16.4 (d, J = 6.6 Hz); 31P NMR (CDCl3, 202 MHz): δ 17.84; IR (film) υmax: 2974, 1729, 1680,

1602, 1549, 1500, 1442, 1326, 1295, 1251, 1125, 1069, 1022, 970, 759 cm-1; HRMS: [M+Na]+

m/z calcd for C19H22NO6PNa+ 414.1077, found 414.1077.

Diethyl (2-(p-tolylcarbamoyl)phenyl)phosphonate (3j, new compound)


7.65 (t, J = 7.8 Hz, 1H), 7.61 (d, J = 8.3 Hz, 2H), 7.56-7.53 (m, 1H), 7.16 (d, J = 8.1 Hz, 2H),


166.3 (d, J = 4.4 Hz), 140.5 (d, J = 11.0 Hz), 135.9, 134.3, 133.0 (d, J = 3.2 Hz), 132.7 (d, J = 8.9

Hz), 130.9 (d, J = 13.3 Hz), 130.2 (d, J = 13.9 Hz), 129.7, 125.2 (d, J = 187.3 Hz), 120.2, 63.5 (d,

J = 6.6 Hz), 21.2, 16.5 (d, J = 5.5 Hz); 31P NMR (CDCl3, 202 MHz): δ 17.94; IR (film) υmax:

2970, 1670, 1603, 1533, 1515, 1405, 1322, 1236, 1142, 1024, 974, 818 cm-1; HRMS: [M+Na]+

m/z calcd for C18H22NO4PNa+ 370.1179, found 370.1180.

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Diethyl (2-((4-(tert-butyl)phenyl)carbamoyl)phenyl)phosphonate (3k, new compound)


7.65-7.61 (m, 3H), 7.55-7.52 (m, 1H), 7.37-7.35 (m, 2H), 4.17-4.12 (m, 4H), 1.31 (s, 9H), 1.29 (t,

J = 7.1 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 166.3 (d, J = 5.5 Hz), 147.6, 140.5 (d, J =

11.0 Hz), 135.8, 133.0 (d, J = 3.3 Hz), 132.8 (d, J = 7.7 Hz), 130.8 (d, J = 13.2 Hz), 130.1 (d, J =

13.3 Hz), 126.0, 125.2 (d, J = 186.7 Hz), 120.0, 63.4 (d, J = 6.6 Hz), 34.6, 31.6, 16.4 (d, J = 6.6


1404, 1325, 1261, 1021, 834, 754, 648 cm-1; HRMS: [M+H]+ m/z calcd for C21H29NO4P+

390.1829, found 390.1829.

Diethyl (2-((4-methoxyphenyl)carbamoyl)phenyl)phosphonate (3l, new compound)


7.66-7.63 (m, 3H), 7.56-7.53 (m, 1H), 6.91-6.88 (m, 2H), 4.18-4.13 (m, 4H), 3.80 (s, 3H), 1.30 (t,

J = 7.0 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 166.2 (d, J = 5.5 Hz), 156.7, 140.5 (d, J =

9.9 Hz), 133.0 (d, J = 2.2 Hz), 132.7 (d, J = 7.7 Hz), 131.7, 130.9 (d, J = 13.2 Hz), 130.2 (d, J =

13.3 Hz), 125.2 (d, J = 187.0 Hz), 121.8, 114.4, 63.5 (d, J = 6.6 Hz), 55.7, 16.5 (d, J = 6.6 Hz); 31P

NMR (CDCl3, 202 MHz): δ 17.99; IR (film) υmax: 3649, 1669, 1510, 1244, 1180, 1142, 1022,

971, 832 cm-1; HRMS: [M+H]+ m/z calcd for C18H23NO5P+ 364.1308, found 364.1306.

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Diethyl (2-((4-(methylthio)phenyl)carbamoyl)phenyl)phosphonate (3m, new compound)


7.67-7.65 (m, 2H), 7.62 (t, J = 7.7 Hz, 1H), 7.54-7.51 (m, 1H), 7.25-7.23 (m, 2H), 4.15-4.10 (m,

4H), 2.46 (s, 3H), 1.28 (t, J = 7.0 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 166.3 (d, J = 4.4

Hz), 140.2 (d, J = 11.1 Hz), 136.1, 133.8, 133.0 (d, J = 3.3 Hz), 132.6 (d, J = 8.8 Hz), 130.8 (d, J

= 13.2 Hz), 130.2 (d, J = 13.7 Hz), 128.0, 125.2 (d, J = 188.2 Hz), 120.7, 63.4 (d, J = 6.6 Hz),

16.8, 16.4 (d, J = 6.6 Hz); 31P NMR (CDCl3, 202 MHz): δ 17.79; IR (film) υmax: 2980, 1670,

1594, 1528, 1496, 1397, 1316, 1232, 1142, 1095, 1022, 972, 819 cm-1; HRMS: [M+Na]+ m/z

calcd for C18H22NO4PSNa+ 402.0899, found 402.0896.

Diethyl (2-((2-iodo-4-(trifluoromethyl)phenyl)carbamoyl)phenyl)phosphonate (3n, new

compound)


1H), 8.05 (s, 1H), 8.00 (dd, J1 = 14.0 Hz, J2 = 7.6 Hz, 1H), 7.73 (t, J = 6.1 Hz, 1H), 7.68-7.64 (m,

2H), 7.61-7.58 (m, 1H), 4.18-4.12 (m, 4H), 1.30 (t, J = 7.2 Hz, 6H); 13C{1H} NMR (CDCl3, 125

MHz): δ 167.3 (d, J = 4.4 Hz), 141.8, 139.8 (d, J = 9.9 Hz), 136.2 (q, J = 4.4 Hz), 133.7 (d, J =

8.8 Hz), 133.0 (d, J = 3.2 Hz), 130.6 (d, J = 13.2 Hz), 129.0 (d, J = 12.1 Hz), 128.1 (q, J = 33.3

Hz), 126.6 (q, J = 3.3 Hz), 126.2 (d, J = 187.0Hz), 123.1 (q, J = 271.7 Hz), 122.3, 89.8, 63.2 (d, J

= 5.5 Hz), 16.6 (d, J = 5.5 Hz); 31P NMR (CDCl3, 202 MHz): δ 16.56; IR (film) υmax: 3369, 2984,

1689, 1603, 1577, 1521, 1321, 1303, 1245, 1171, 1126, 1023, 970, 750 568 cm-1; HRMS: [M+H]+

m/z calcd for C18H19F3INO4P+ 528.0034, found 528.0034.

S17

Diethyl (2-((3-chloro-4-fluorophenyl)carbamoyl)phenyl)phosphonate (3o, new compound)

White solid; 60.1 mg, 78% yield; 1H NMR (CDCl3, 500 MHz): δ 9.69 (s, 1H), 7.93 (dd, J1 = 6.7

Hz, J2 = 2.5 Hz, 1H), 7.82 (t, J = 6.7 Hz, 1H), 7.78 (dd, J1 = 14.2 Hz, J2 = 7.7 Hz, 1H), 7.61 (t, J =

7.5 Hz, 1H), 7.54-7.50 (m, 2H), 7.05 (t, J = 8.9 Hz, 1H), 4.16-4.11 (m, 4H), 1.30 (t, J = 7.1 Hz,

6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 166.4 (d, J = 4.4 Hz), 154.9 (d, J = 246.4 Hz), 139.8 (d,

J = 11.0 Hz), 135.3 (d, J = 3.3 Hz), 132.9 (d, J = 2.2 Hz), 132.6 (d, J = 7.8 Hz), 130.8 (d, J = 14.3

Hz), 130.4 (d, J = 14.3 Hz), 125.3 (d, J = 187.1 Hz), 122.3, 121.1 (d, J = 18.8 Hz), 119.8 (d, J =

7.7 Hz), 116.6 (d, J = 22.0 Hz), 63.5 (d, J = 6.6 Hz), 16.4 (d, J = 6.6 Hz); 31P NMR (CDCl3, 202

MHz): δ 17.64; IR (film) υmax: 2960, 1672, 1579, 1514, 1428, 1296, 1250, 1024, 985, 772, 692

cm-1; HRMS: [M+Na]+ m/z calcd for C17H18ClFNO4PNa+ 408.0538, found 408.0536.

Diethyl (2-(naphthalen-1-ylcarbamoyl)phenyl)phosphonate (3p, new compound)


1H), 8.04 (d, J = 8.0 Hz, 1H), 7.98 (dd, J1 = 14.2 Hz, J2 = 7.7 Hz, 1H), 7.91 (t, J = 6.8 Hz, 1H),

7.86 (dd, J1 = 6.7 Hz, J2 = 1.9 Hz, 1H), 7.72 (d, J = 8.8 Hz, 1H), 7.67 (t, J = 7.8 Hz, 1H),

7.60-7.57 (m, 1H), 7.54-7.46 (m, 3H), 4.18-4.11 (m, 4H), 1.27 (t, J = 6.9 Hz, 6H); 13C{1H} NMR

(CDCl3, 125 MHz): δ 167.4 (d, J = 4.4 Hz), 140.5 (d, J = 10.0 Hz), 134.3, 130.1 (d, J = 8.7 Hz),

130.06 (d, J = 3.0 Hz), 132.97, 130.5 (d, J = 13.6 Hz), 130.2 (d, J = 13.9 Hz), 128.8, 127.3, 126.4,

126.2, 126.0, 125.9, 125.3 (d, J = 186.7 Hz), 121.4, 120.4, 63.4 (d, J = 6.4 Hz), 16.4 (d, J = 6.4


1550, 1506, 1472, 1394, 1360, 1294, 1233, 1143, 1024, 969, 748 cm-1; HRMS: [M+H]+ m/z calcd

for C21H23NO4P+ 384.1359 found 384.1359.

S18

Diethyl (2-(naphthalen-2-ylcarbamoyl)phenyl)phosphonate (3q, new compound)


1H), 7.94 (t, J = 6.4 Hz, 1H), 7.90 (dd, J1 = 14.3 Hz, J2 = 7.7 Hz, 1H), 7.84 (d, J = 8.1 Hz, 1H),

7.81 (d, J = 8.8 Hz, 1H), 7.79 (d, J = 8.2 Hz, 1H), 7.69-7.65 (m, 2H), 7.58-7.55 (m, 1H), 7.46 (t, J

= 7.5 Hz, 1H), 7.40 (t, J = 7.5 Hz, 1H), 4.19-4.13 (m, 4H), 1.29 (t, J = 7.1 Hz, 6H); 13C{1H} NMR

(CDCl3, 125 MHz): δ 166.5 (d, J = 4.4 Hz), 140.3 (d, J = 10.0 Hz), 136.0, 134.1, 130.0 (d, J = 3.3

Hz), 132.6 (d, J = 7.7 Hz), 132.98, 132.97 (d, J = 13.2 Hz), 130.3 (d, J = 13.4 Hz), 128.9, 128.1,

127.7, 126.6, 125.3 (d, J = 187.3 Hz), 125.2, 120.1, 116.9, 63.4 (d, J = 6.6 Hz), 16.4 (d, J = 6.6


1346, 1235, 1142, 1023, 967, 797, 796, 773 cm-1; HRMS: [M+H]+ m/z calcd for C21H23NO4P+

384.1359 found 384.1359.

Diethyl (2-(pyridin-2-ylcarbamoyl)phenyl)phosphonate (3r, new compound)


1H), 8.14-8.12 (m, 1H), 7.99 (dd, J1 = 14.2 Hz, J2 = 7.6 Hz, 1H), 7.74-7.71 (m, 2H), 7.62 (t, J =

7.5 Hz, 1H), 7.58-7.55 (m, 1H), 7.02-6.99 (m, 1H), 4.17-4.10 (m, 4H), 1.26 (t, J = 7.2 Hz, 6H);

13C{1H} NMR (CDCl3, 125 MHz): δ 167.4 (d, J = 4.4 Hz), 151.8, 148.2, 140.2 (d, J = 9.9 Hz),

138.5, 133.7 (d, J = 9.4 Hz), 132.9 (d, J = 2.6 Hz), 130.3 (d, J = 14.1 Hz), 129.4 (d, J = 13.1 Hz),

125.8 (d, J = 187.7 Hz), 120.1, 114.3, 63.2 (d, J = 5.5 Hz), 16.3 (d, J = 6.6 Hz); 31P NMR (CDCl3,

202 MHz): δ 16.69; IR (film) υmax: 2960, 1683, 1579, 1533, 1433, 1308, 1243, 1144, 1022, 967,

781 cm-1; HRMS: [M+H]+ m/z calcd for C16H20N2O4P+ 335.1155, found 335.1155.

S19

Diethyl (E/Z)-(2-(styrylcarbamoyl)phenyl)phosphonate (3s, new compound)

Colorless oil; 53.8 mg, 75% yield; 1H NMR (CDCl3, 500 MHz): δ 8.61 (d, J = 10.7 Hz, 1H),7.97-7.94 (m, 1H), 7.70-7.68 (m, 1H), 7.63-7.61 (m, 1H), 7.56-7.53 (m, 1H), 7.34-7.30 (m, 4H),7.20-7.17 (m, 1H), 7.15-7.11 (m, 1H), 5.87 (d, J = 9.7 Hz, 1H), 4.02-3.97 (m, 4H), 1.81 (t, J = 7.1Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 166.8 (d, J = 4.9 Hz), 139.3 (d, J = 9.1 Hz), 135.7,135.6 (d, J = 9.4 Hz), 132.9 (d, J = 2.9 Hz), 130.3 (d, J = 13.7 Hz), 129.8 (d, J = 12.8 Hz), 129.2,128.2, 127.2, 125.8 (d, J = 187.2 Hz), 122.1, 111.8, 63.2 (d, J = 6.6 Hz), 16.3 (d, J = 5.6 Hz); 31PNMR (CDCl3, 202 MHz): δ 16.71; IR (film) υmax: 3253, 2977, 2899, 1675, 1598, 1540, 1437,1389, 1321, 1235, 1022, 985, 754 cm-1; HRMS: [M+Na]+ m/z calcd for C19H22NO4PNa+

382.1179, found 382.1179.

Methyl 3-(diethoxyphosphoryl)-4-(phenylcarbamoyl)benzoate (3t, new compound)

White solid; 67.3 mg, 86% yield; 1H NMR (CDCl3, 500 MHz): δ 9.27 (s, 1H), 8.53 (dd, J1 = 14.8Hz, J2 = 1.3 Hz, 1H), 8.28 (d, J = 8.0 Hz, 1H), 7.97 (dd, J1 = 8.0 Hz, J2 = 5.2 Hz, 1H), 7.73 (d, J =7.8 Hz, 2H), 7.36 (t, J = 7.6 Hz, 2H), 7.15 (t, J = 7.4 Hz, 1H) 4.22-4.16 (m, 4H), 3.97 (s, 3H), 1.32(t, J = 7.0 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 165.7 (d, J = 1.8 Hz), 165.5 (d, J = 4.6Hz), 144.0 (d, J = 10.9 Hz), 138.2, 133.9 (d, J = 10.0 Hz), 133.8 (d, J = 2.7 Hz), 131.7 (d, J = 13.6Hz), 131.3 (d, J = 12.7 Hz), 129.3, 126.1 (d, J = 189.0 Hz), 125.0, 120.3, 63.8 (d, J = 6.4 Hz), 52.9,16.5 (d, J = 6.4 Hz); 31P NMR (CDCl3, 202 MHz): δ 16.31; IR (film) υmax: 2961, 1732, 1701,1682, 1645, 1545, 1522, 1411, 1331, 1271, 1142, 1022, 970, 762 cm-1; HRMS: [M+Na]+ m/zcalcd for C19H22NO6PNa+ 414.1077, found 414.1077.

Diethyl (4-methyl-2-(phenylcarbamoyl)phenyl)phosphonate (3u, new compound)


S20

Hz, J2 = 7.8 Hz, 1H), 7.71 (d, J = 8.0 Hz, 2H), 7.69 (d, J = 4.8 Hz, 1H), 7.34 (t, J = 7.0 Hz, 3H),

7.11 (t, J = 7.3 Hz, 1H), 4.14-4.09 (m, 4H), 2.42 (s, 3H), 1.27 (t, J = 7.0 Hz, 6H); 13C{1H} NMR

(CDCl3, 125 MHz): δ 166.6 (d, J = 5.5 Hz), 143.8 (d, J = 2.2 Hz), 140.2 (d, J = 11.0 Hz), 138.5,

132.9 (d, J = 8.8 Hz), 131.5 (d, J = 13.5 Hz), 130.8 (d, J = 14.3 Hz), 129.2, 124.6, 121.9 (d, J =

189.4 Hz), 120.1, 63.3 (d, J = 6.7 Hz), 21.6, 16.4 (d, J = 6.7 Hz); 31P NMR (CDCl3, 202 MHz): δ

18.60; IR (film) υmax: 3255, 2981, 1679, 1600, 1543, 1500, 1442, 1393, 1324, 1232, 1025, 970,

756, 694 cm-1; HRMS: [M+Na]+ m/z calcd for C18H22NO4PNa+ 370.1179, found 370.1178.

Diethyl (4-methoxy-2-(phenylcarbamoyl)phenyl)phosphonate (3v, new compound)


Hz, J2 = 8.6 Hz, 1H), 7.72 (d, J = 7.7 Hz, 2H), 7.40 (dd, J1 = 4.5 Hz, J2 = 2.7 Hz, 1H), 7.34 (t, J =

7.6 Hz, 2H), 7.12 (t, J = 7.4 Hz, 1H), 7.02 (dt, J1 = 8.5 Hz, J2 = 2.5 Hz, 1H), 4.14-4.08 (m, 4H),

3.87 (s, 3H), 1.27 (t, J = 7.1 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 166.1 (d, J = 4.4 Hz),

163.1 (d, J = 3.3 Hz), 142.4 (d, J = 12.1 Hz), 138.4, 135.0 (d, J = 8.8 Hz), 129.2, 124.6, 120.2,

116.4 (d, J = 194.0 Hz), 116.1 (d, J = 15.4 Hz), 116.0 (d, J = 14.3 Hz), 63.2 (d, J = 6.6 Hz), 55.8,

16.4 (d, J = 5.5 Hz); 31P NMR (CDCl3, 202 MHz): δ 18.89; IR (film) υmax: 2972, 1663, 1562,


C18H22NO5PNa+ 386.1128, found 386.1124.

Diethyl (4-chloro-2-(phenylcarbamoyl)phenyl)phosphonate (3w, new compound)


S21

Hz, J2 = 2.0 Hz, 1H), 7.82 (dd, J1 = 13.8 Hz, J2 = 8.3 Hz, 1H), 7.70 (d, J = 7.9 Hz, 2H), 7.51 (dt, J1

= 8.2 Hz, J2 = 2.4 Hz, 1H), 7.35 (t, J = 8.1 Hz, 2H), 7.14 (t, J = 7.4 Hz, 1H), 4.14-4.13 (m, 4H),

1.29 (t, J = 7.1 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 164.9 (d, J = 4.4 Hz), 161.9 (d, J =

11.0 Hz), 139.7 (d, J = 3.3 Hz), 138.2, 134.3 (d, J = 8.8 Hz), 131.1 (d, J = 13.2 Hz), 130.3 (d, J =

15.4 Hz), 129.3, 124.9, 123.7 (d, J = 190.4 Hz), 120.2, 63.7 (d, J = 6.6 Hz), 16.4 (d, J = 5.5 Hz);

31P NMR (CDCl3, 202 MHz): δ 16.90; IR (film) υmax: 2965, 1672, 1589, 1532, 1481, 1395, 1318,

1225, 1089, 1019, 962, 826, 595 cm-1; HRMS: [M+Na]+ m/z calcd for C17H19ClNO4PNa+

390.0632, found 390.0631.

Diethyl (4-bromo-2-(phenylcarbamoyl)phenyl)phosphonate (3x, new compound)


Hz, J2 = 1.8 Hz, 1H), 7.74 (dd, J1 = 13.7 Hz, J2 = 8.3 Hz, 1H), 7.71-7.67 (m, 3H), 7.35 (t, J = 7.6

Hz, 2H), 7.14 (t, J = 7.5 Hz, 1H), 4.17-4.12 (m, 4H), 1.29 (t, J = 7.0 Hz, 6H); 13C{1H} NMR


133.9 (d, J = 14.3 Hz), 133.3 (d, J = 14.4 Hz), 129.3, 128.1 (d, J = 4.4 Hz), 124.9, 124.2 (d, J =

189.8 Hz), 120.2, 63.7 (d, J = 6.6 Hz), 16.4 (d, J = 6.6 Hz); 31P NMR (CDCl3, 202 MHz): δ 17.03;

IR (film) υmax: 2962, 1680, 1599, 1544, 1500, 1322, 1235, 1067, 1021, 973, 770, 693 cm-1;

HRMS: [M+Na]+ m/z calcd for C17H19BrNO4PNa+ 434.0127, found 434.1027.

Diethyl (2-(phenylcarbamoyl)thiophen-3-yl)phosphonate (3y, new compound)


Hz, J2 = 0.7 Hz, 2H), 7.55 (dd, J1 = 5.5 Hz, J2 = 2.2 Hz, 1H), 7.34 (t, J = 7.6 Hz, 2H), 7.30 (t, J =

S22

4.8 Hz, 1H), 7.11 (t, J = 7.3 Hz, 1H), 4.24-4.11 (m, 4H), 1.34 (t, J = 7.1 Hz, 6H); 13C{1H} NMR


130.4 (d, J = 18.7 Hz), 129.1, 125.3 (d, J = 187.7 Hz), 124.5, 120.3, 63.5 (d, J = 5.5 Hz), 16.4 (d, J

= 6.6 Hz); 31P NMR (CDCl3, 202 MHz): δ 14.03; IR (film) υmax: 2983, 1772, 1604, 1553, 1492,

1462, 1390, 1285, 1183, 1114, 1019, 997, 754 cm-1; HRMS: [M+Na]+ m/z calcd for

C15H18NO4PSNa+ 362.0586, found 362.0586.

Dimethyl (2-(phenylcarbamoyl)phenyl)phosphonate (4a, CAS NO.: 460836-90-0)


7.71 (d, J = 8.1 Hz, 2H), 7.64 (t, J = 7.7 Hz, 1H), 7.56-7.53 (m, 1H), 7.34 (t, J = 7.4 Hz, 2H), 7.13

(t, J = 7.3 Hz, 1H), 3.77 (t, J = 11.0 Hz, 6H); 13C{1H} NMR (CDCl3, 125 MHz): δ 166.5 (d, J =

4.4 Hz), 140.6 (d, J = 10.3 Hz), 138.4, 133.2 (d, J = 2.4 Hz), 133.0 (d, J = 7.9 Hz), 130.5 (d, J =

13.3 Hz), 130.3 (d, J = 14.1 Hz), 129.3, 124.8, 134.2 (d, J = 188.0 Hz), 120.3, 53.8 (d, J = 6.1 Hz);

31P NMR (CDCl3, 202 MHz): δ 20.33; IR (film) υmax: 3251, 2960, 1670, 1601, 1544, 1492, 1442,

1324, 1241, 1031, 836, 788, 758 cm-1; HRMS: [M+Na]+ m/z calcd for C15H16NO4PNa+ 328.0709,

found 328.0709.

Diisopropyl (2-(phenylcarbamoyl)phenyl)phosphonate (4b, CAS NO.: 60815-47-6)


7.71 (d, J = 8.2 Hz, 2H), 7.58 (t, J = 7.5 Hz, 1H), 7.50 (t, J = 8.2 Hz, 1H), 7.31 (t, J = 7.8 Hz, 2H),

7.08 (t, J = 7.2 Hz, 1H), 4.77-4.72 (m, 2H), 1.27-1.24 (m, 12H); 13C{1H} NMR (CDCl3, 125

MHz): δ 166.3 (d, J = 5.5 Hz), 140.1 (d, J = 11.0 Hz), 138.5, 132.63 (d, J = 3.3 Hz), 132.57 (d, J

S23

= 9.1 Hz), 130.9 (d, J = 13.2 Hz), 130.0 (d, J = 14.1 Hz), 129.0, 126.4 (d, J = 188.1 Hz), 124.4,

120.1, 72.4 (d, J = 6.5 Hz), 24.1 (d, J = 4.3 Hz), 23.9 (d, J = 4.4 Hz); 31P NMR (CDCl3, 202

MHz): δ 15.81; IR (film) υmax: 3261, 3063, 2979, 2934, 1680, 1601, 1544, 1499, 1442, 1386,

1375, 1322, 1230, 1142, 1105, 1072, 995, 756 570 cm-1; HRMS: [M+Na]+ m/z calcd for

C19H24NO4PNa+ 384.1335, found 384.1334.

Diisopropyl (2-(phenylcarbamoyl)thiophen-3-yl)phosphonate (4c, new compound)

White solid; 63.1 mg, 86% yield; 1H NMR (CDCl3, 500 MHz): δ 12.25 (s, 1H), 7.81 (d, J = 7.7

Hz, 2H), 7.53 (dd, J1 = 5.1 Hz, J2 = 2.3 Hz, 1H), 7.35-7.30 (m, 3H), 7.11 (t, J = 7.4 Hz, 1H),

4.78-4.72 (m, 2H), 1.39 (d, J = 6.2 Hz, 6H), 1.26 (d, J = 6.2 Hz, 6H); 13C{1H} NMR (CDCl3, 125

MHz): δ 158.9 (d, J = 3.3 Hz), 150.9 (d, J = 20.7 Hz), 138.9, 133.1 (d, J = 12.1 Hz), 130.2 (d, J =

19.0 Hz), 129.1, 127.0 (d, J = 189.1 Hz), 124.4, 120.4, 72.7 (d, J = 5.6 Hz), 24.2 (d, J = 4.2 Hz),

23.9 (d, J = 4.4 Hz); 31P NMR (CDCl3, 202 MHz): δ 11.53 IR (film) υmax: 2962, 1660, 1627,

1565, 1489, 1447, 1398, 1324, 1270, 1225, 1167, 1020, 976, 844, 758 cm-1; HRMS: [M+Na]+ m/z

calcd for C17H22NO4PSNa+ 390.0899, found 390.0904.

Dibutyl (2-(phenylcarbamoyl)phenyl)phosphonate (4d, new compound)


7.72 (d, J = 8.3 Hz, 2H), 7.60 (t, J = 7.7 Hz, 1H), 7.51 (t, J = 7.7 Hz, 1H), 7.33-7.30 (m, 2H), 7.09

(t, J = 6.6 Hz, 1H), 4.07-4.03 (m, 4H), 1.61-1.56 (m, 4H), 1.32-1.26 (m, 4H), 0.83-0.80 (m, 6H);

13C{1H} NMR (CDCl3, 125 MHz): δ 166.3 (d, J = 5.3 Hz), 140.2 (d, J = 10.0 Hz), 138.5, 132.9

(d, J = 2.2 Hz), 132.5 (d, J = 7.7 Hz), 130.8 (d, J = 13.6 Hz), 130.1 (d, J = 13.5 Hz), 129.0, 125.2

S24

(d, J = 188.0 Hz), 124.5, 120.0, 67.1 (d, J = 6.6 Hz), 32.5 (d, J = 6.6 Hz), 18.8, 13.6; 31P NMR

(CDCl3, 202 MHz): δ 20.33; IR (film) υmax: 3254, 3133, 3061, 2961, 2873, 1679, 1602, 1545,


C21H28NO4PNa+ 412.1648, found 412.1649.

Ethyl phenyl(2-(phenylcarbamoyl)phenyl)phosphinate (4f, new compound)


7.72-7.68 (m, 4H), 7.63-7.59 (m, 2H), 7.56-7.53 (m, 1H), 7.49-7.46 (m, 1H), 7.42-7.39 (m, 2H),

7.32 (t, J = 7.9 Hz, 2H), 7.11 (t, J = 7.3 Hz, 1H), 4.14-4.07 (m, 1H), 3.97-3.90 (m, 1H), 1.21 (t, J =

7.2 Hz, 3H); 13C{1H} NMR (CDCl3, 125 MHz): δ 166.2 (d, J = 4.4 Hz), 140.6 (d, J = 10.0 Hz),

138.5, 133.2 (d, J = 2.7 Hz), 132.8 (d, J = 2.2 Hz), 132.5 (d, J = 10.8 Hz), 132.1 (d, J = 10.5 Hz),

131.2 (d, J = 11.2 Hz), 130.1 (d, J = 13.0 Hz), 129.2 (d, J = 134.7 Hz), 129.1, 128.9 (d, J = 13.3

Hz), 128.8 (d, J = 136.8 Hz), 124.5, 120.0, 62.1 (d, J = 5.6 Hz), 16.4 (d, J = 6.6 Hz); 31P NMR


1260, 1142, 1032, 799, 758, 693 cm-1; HRMS: [M+H]+ m/z calcd for C21H21NO3P+ 366.1254,

found 366.1256.

3-(Diphenylphosphoryl)-N-phenylthiophene-2-carboxamide (4g, new compound)

White solid; 69.3 mg, 86% yield; 1H NMR (CDCl3, 500 MHz): δ 12.49 (s, 1H), 7.77 (d, J = 7.7

Hz, 2H), 8.67-8.64 (m, 4H), 7.60-7.58 (m, 2H), 7.51-7.48 (m, 5H), 7.30 (t, J = 7.7 Hz, 2H), 7.08 (t,

S25

J = 7.3 Hz, 1H), 6.70 (t, J = 5.2 Hz, 1H); 13C{1H} NMR (CDCl3, 125 MHz): δ 159.1 (d, J = 2.2

Hz), 152.6 (d, J = 11.0 Hz), 138.9, 133.5 (d, J = 16.5 Hz), 133.1 (d, J = 2.9 Hz), 132.0 (d, J = 10.8

Hz), 131.4 (d, J = 108.9 Hz), 129.9 (d, J = 16.5 Hz), 129.6 (d, J = 101.4 Hz), 129.2 (d, J = 13.1

Hz), 129.0, 124.4, 120.4; 31P NMR (CDCl3, 202 MHz): δ 29.27; IR (film) υmax: 2960, 1716,

1688, 1601, 1533, 1408, 1279, 1260, 1178, 1143, 1112, 1024, 971, 770 cm-1; HRMS: [M+H]+ m/z

calcd for C23H19NO2PS+ 404.0869, found 404.0869.

2-(Diphenylphosphoryl)-N-phenylbenzamide (4h, new compound)

White solid; 66.7 mg, 84% yield; 1H NMR (CDCl3, 500 MHz): δ 10.54 (s, 1H), 8.08-8.06 (m,

1H), 7.68-7.63 (m, 5H), 7.51-7.49 (m, 2H), 7.44-7.39 (m, 7H), 7.21-7.19 (m, 2H), 7.14-7.10 (m,

1H), 7.04-7.01 (m, 1H); 13C{1H} NMR (CDCl3, 125 MHz): δ 165.4 (d, J = 4.4 Hz), 141.3 (d, J =

8.3 Hz), 137.9, 133.2 (d, J = 11.9 Hz), 132.8 (d, J = 3.3 Hz), 132.4 (d, J = 3.3 Hz), 132.3 (d, J =

8.9 Hz), 131.6 (d, J = 10.2 Hz), 130.5 (d, J = 94.8 Hz), 130.1, 129.6 (d, J = 98.0 Hz), 128.7 (d, J =

12.5 Hz), 128.5, 124.1, 120.1; 31P NMR (CDCl3, 202 MHz): δ 34.45; IR (film) υmax: 3062, 1670,

1601, 1549, 1499, 1438, 1325, 1180, 1120, 1075, 756, 727, 692, 542 cm-1; HRMS: [M+H]+ m/z

calcd for C25H21NO2P+ 398.1304, found 398.1302.

N-(4-Chlorophenyl)-2-(diphenylphosphoryl)benzamide (4i, new compound)


Hz, J2 = 4.1 Hz, 1H), 7.70-7.67 (m, 1H), 7.66-7.62 (m, 4H), 7.54-7.51 (m, 2H), 7.46-7.40 (m, 7H),

7.19-7.16 (m, 2H), 7.12 (dd, J1 = 14.0 Hz, J2 = 7.3 Hz, 1H); 13C{1H} NMR (CDCl3, 125 MHz): δ

165.6 (d, J = 3.8 Hz), 141.1 (d, J = 8.8 Hz), 136.8, 133.5 (d, J = 11.8 Hz), 133.0 (d, J = 2.2 Hz),

S26

132.7 (d, J = 3.2 Hz), 132.5 (d, J = 9.4 Hz), 131.7 (d, J = 9.9 Hz), 130.5 (d, J = 12.1 Hz), 130.4 (d,

J = 106.4 Hz), 129.14, 129.08 (d, J = 105.7 Hz), 128.9 (d, J = 12.3 Hz), 128.7, 121.5; 31P NMR


1258, 1152, 1064, 1030, 976, 755 cm-1; HRMS: [M+H]+ m/z calcd for C25H20ClNO2P+ 432.0915,

found 432.0912.

2-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-N-(m-tolyl)benzamide (6a, new compound)


2H), 7.54-7.51 (m, 1H), 7.46 (t, J = 8.0 Hz, 2H), 7.42 (d, J = 8.1 Hz, 1H), 7.24 (t, J = 7.8 Hz, 1H),

6.96 (d, J = 7.7 Hz, 1H), 2.35 (s, 3H), 1.25 (s, 12H); 13C{1H} NMR (CDCl3, 125 MHz): δ 166.0,

139.2, 135.3, 138.1, 132.0, 129.1, 129.0, 127.2, 125.6, 121.1, 117.5, 83.7, 25.2, 21.7; IR (film)

υmax: 2978, 1748, 1688, 1649, 1612, 1544, 1489 1281, 1124, 1030, 848, 780, 692 cm-1; HRMS:

[M+Na]+ m/z calcd for C20H24BNO3Na+ 360.1741, found 360.1740.

N-Phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene-2-carboxamide (6b, new

compound)

White solid; 42.8 mg, 65% yield; 1H NMR (CDCl3, 500 MHz): δ 10.75 (s, 1H), 7.73-7.71 (m,

2H), 7.51 (s, 2H), 7.38-7.35 (m, 2H), 7.14-7.11 (m, 1H), 1.45 (s, 12H); 13C{1H} NMR (CDCl3,

125 MHz): δ 160.5, 151.9, 139.1, 136.4, 130.1, 129.3, 124.2, 120.0, 85.6, 25.1; IR (film) υmax:

2976, 1754, 1744, 1678, 1642, 1609, 1558, 1482, 1280, 1142, 1021, 853, 778 cm-1; HRMS:

[M+H]+ m/z calcd for C17H21BNO3S+ 330.1330, found 330.1328.

S27

8. 1H, 13C and 31P spectrum for all the products.

10 9 8 7 6 5 4 3 2 1 0 ppm

1.271

1.282

1.294

4.119

4.132

4.144

4.155

4.157

4.167

4.169

7.113

7.125

7.137

7.331

7.344

7.357

7.526

7.528

7.532

7.533

7.539

7.540

7.544

7.546

7.551

7.553

7.557

7.558

7.627

7.640

7.652

7.715

7.727

7.856

7.867

7.879

7.891

7.892

7.904

7.905

9.152

6.00

4.02

0.99

2.01

1.02

1.00

2.00

2.02

1.00

NH

OPh

PO

EtOEtO

1H NMR spectrum of compound 3a

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.43

16.47

63.46

63.50

120.18

124.61

124.69

125.85

129.23

130.21

130.30

130.75

130.84

132.73

132.79

133.04

133.06

138.49

140.36

140.43

166.46

166.49

NH

OPh

PO

EtOEtO

13C NMR spectrum of compound 3a

S28

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

17.78

NH

OPh

PO

EtOEtO

31P NMR spectrum of compound 3a

10 9 8 7 6 5 4 3 2 1 0 ppm

1.281

1.293

1.305

2.353

4.126

4.138

4.150

4.162

4.175

6.938

6.950

7.213

7.226

7.239

7.511

7.525

7.538

7.543

7.555

7.626

7.639

7.651

7.854

7.867

7.876

7.880

7.892

7.904

9.089

6.00

2.98

4.00

1.00

1.00

3.01

1.01

1.99

1.00

NH

OPO

EtOEtO

Me

1H NMR spectrum of compound 3b

S29

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.40

16.45

21.75

63.42

63.46

117.25

120.71

124.54

125.49

125.78

129.01

130.13

130.22

130.74

130.83

132.67

132.73

133.00

133.01

138.37

139.06

140.42

140.49

166.36

166.40

NH

OPO

EtOEtO

Me

13C NMR spectrum of compound 3b

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

17.87

NH

OPO

EtOEtO

Me

31P NMR spectrum of compound 3b

S30

10 9 8 7 6 5 4 3 2 1 0 ppm

1.293

1.305

1.317

2.313

4.125

4.137

4.149

4.162

4.174

7.080

7.092

7.104

7.190

7.202

7.225

7.238

7.251

7.538

7.543

7.551

7.556

7.563

7.568

7.630

7.643

7.656

7.813

7.824

7.835

7.905

7.918

7.929

7.941

8.015

8.028

8.515

6.00

3.00

4.00

1.00

1.00

1.00

1.00

1.00

1.00

1.00

0.99

1.00

NH

OPO

EtOEtO

Me

1H NMR spectrum of compound 3c

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.41

16.46

18.04

63.30

63.34

123.05

124.73

125.54

125.97

126.81

129.97

130.06

130.16

130.25

130.34

130.75

132.93

132.98

136.10

140.53

140.60

166.80

166.83

NH

OPO

EtOEtO

Me

13C NMR spectrum of compound 3c

S31

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

17.57

NH

OPO

EtOEtO

Me

31P NMR spectrum of compound 3c

10 9 8 7 6 5 4 3 2 1 0 ppm

1.267

1.279

1.291

4.107

4.112

4.118

4.124

4.130

4.137

4.142

4.149

4.154

4.160

4.167

4.171

7.001

7.014

7.027

7.344

7.357

7.369

7.545

7.559

7.568

7.573

7.580

7.585

7.629

7.642

7.654

7.699

7.708

7.720

7.981

7.994

8.005

8.018

8.355

8.419

8.433

6.00

4.01

1.00

1.01

2.00

1.00

0.99

1.00

0.96

1.00

NH

OPO

EtOEtO

Br

1H NMR spectrum of compound 3d

S32

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.45

16.49

63.11

63.15

114.36

122.79

125.38

125.92

126.62

128.53

129.05

129.14

130.22

130.31

132.65

132.92

132.94

133.69

133.75

136.00

140.24

140.31

167.08

NH

OPO

EtOEtO

Br

13C NMR spectrum of compound 3d

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.28

NH

OPO

EtOEtO

Br

31P NMR spectrum of compound 3d

S33

10 9 8 7 6 5 4 3 2 1 0 ppm

1.285

1.297

1.309

4.123

4.128

4.136

4.140

4.148

4.152

4.154

4.160

4.166

4.172

4.177

4.184

4.189

6.878

6.880

6.891

6.892

6.903

6.905

7.382

7.395

7.408

7.563

7.569

7.576

7.580

7.588

7.593

7.642

7.654

7.667

7.732

7.741

7.752

7.801

7.803

7.814

7.816

7.988

8.001

8.011

8.024

8.179

6.02

4.01

1.00

1.01

1.00

1.01

1.00

1.00

1.00

1.00

1.00

NH

OPO

EtOEtO

I

1H NMR spectrum of compound 3e

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.52

16.57

63.14

63.18

91.14

123.27

125.47

126.70

126.82

129.00

129.08

129.41

130.23

130.32

132.95

133.74

133.80

138.62

139.21

140.27

140.34

167.07

NH

OPO

EtOEtO

I

13C NMR spectrum of compound 3e

S34

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.85

NH

OPO

EtOEtO

I

31P NMR spectrum of compound 3e

10 9 8 7 6 5 4 3 2 1 0 ppm

1.270

1.282

1.294

4.103

4.108

4.110

4.115

4.120

4.122

4.133

4.135

4.144

4.147

4.156

4.159

4.164

6.999

7.004

7.008

7.019

7.029

7.033

7.518

7.520

7.523

7.525

7.530

7.532

7.536

7.538

7.543

7.545

7.548

7.550

7.617

7.620

7.630

7.632

7.640

7.643

7.645

7.680

7.683

7.688

7.692

7.695

7.699

7.703

7.830

5.99

4.00

2.00

1.01

1.00

2.00

2.00

0.99

NH

OPO

EtOEtO F

1H NMR spectrum of compound 3f

S35

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.39

16.44

63.44

63.49

115.72

115.87

121.86

121.91

124.56

125.80

130.24

130.33

130.76

130.84

132.61

132.67

133.00

133.01

134.56

134.57

140.10

140.17

158.84

160.45

166.33

166.36

NH

OPO

EtOEtO F

13C NMR spectrum of compound 3f

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

17.78

17.82

NH

OPO

EtOEtO F

31P NMR spectrum of compound 3f

S36

10 9 8 7 6 5 4 3 2 1 0 ppm

1.271

1.283

1.295

4.107

4.108

4.120

4.132

4.143

4.145

4.155

4.157

7.279

7.293

7.523

7.528

7.535

7.539

7.548

7.552

7.620

7.632

7.645

7.680

7.695

7.823

7.835

7.847

7.859

7.870

9.436

6.00

4.00

2.00

1.02

1.01

2.01

1.99

0.99

NH

OPO

EtOEtO Cl

1H NMR spectrum of compound 3g

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.40

16.44

63.48

63.52

121.37

124.58

125.82

129.17

129.50

130.32

130.41

130.82

130.91

132.57

132.62

133.00

133.02

137.14

139.97

140.05

166.37

166.40

NH

OPO

EtOEtO Cl

13C NMR spectrum of compound 3g

S37

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

17.80

NH

OPO

EtOEtO Cl

31P NMR spectrum of compound 3g

10 9 8 7 6 5 4 3 2 1 0 ppm

1.277

1.289

1.301

4.104

4.111

4.116

4.123

4.127

4.136

4.145

4.148

4.153

4.160

4.165

7.523

7.528

7.535

7.541

7.549

7.560

7.569

7.618

7.631

7.643

7.799

7.812

7.822

7.836

7.846

7.859

7.869

9.765

6.00

4.00

3.00

1.00

3.99

0.99

NH

OPO

EtOEtO CF3

1H NMR spectrum of compound 3h

S38

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.39

16.43

63.50

63.54

119.82

121.66

123.46

124.71

125.26

125.87

125.95

126.08

126.30

126.31

126.34

126.37

126.39

126.52

127.07

130.44

130.53

130.81

130.89

132.61

132.66

132.97

132.99

139.80

139.88

141.63

166.68

166.72

NH

OPO

EtOEtO CF3

13C NMR spectrum of compound 3h

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

17.78

17.82

NH

OPO

EtOEtO CF3

31P NMR spectrum of compound 3h

S39

10 9 8 7 6 5 4 3 2 1 0 ppm

1.264

1.275

1.287

3.885

4.110

4.112

4.122

4.124

4.135

4.146

4.149

4.158

4.161

7.537

7.542

7.550

7.555

7.562

7.566

7.632

7.645

7.658

7.805

7.819

7.830

7.843

7.854

7.867

7.878

7.889

8.001

8.015

9.637

5.99

3.00

4.00

1.00

1.00

3.99

2.00

1.00

NH

OPO

EtOEtO CO2Me

1H NMR spectrum of compound 3i

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.40

16.44

52.20

63.52

63.56

119.31

124.69

125.91

125.93

130.47

130.56

130.93

131.01

132.57

132.63

133.03

133.05

139.82

139.89

142.69

166.60

166.64

166.89

NH

OPO

EtOEtO CO2Me

13C NMR spectrum of compound 3i

S40

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

17.84

NH

OPO

EtOEtO CO2Me

31P NMR spectrum of compound 3i

10 9 8 7 6 5 4 3 2 1 0 ppm

1.284

1.296

1.308

2.330

4.131

4.143

4.154

4.166

4.180

7.149

7.162

7.532

7.537

7.544

7.549

7.550

7.557

7.561

7.601

7.615

7.636

7.649

7.662

7.874

7.881

7.894

7.904

7.916

9.056

6.00

2.99

4.00

2.00

1.00

1.99

0.99

2.00

1.00

NH

OPO

EtOEtO Me

1H NMR spectrum of compound 3j

S41

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.44

16.48

21.16

63.43

63.48

120.17

124.56

125.80

129.73

130.13

130.22

130.81

130.90

132.72

132.78

133.02

133.04

134.28

135.94

140.45

140.52

166.26

166.29

NH

OPO

EtOEtO Me

13C NMR spectrum of compound 3j

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

17.94

NH

OPO

EtOEtO Me

31P NMR spectrum of compound 3j

S42

10 9 8 7 6 5 4 3 2 1 0 ppm

1.282

1.293

1.308

4.124

4.136

4.148

4.160

4.173

7.347

7.352

7.355

7.363

7.366

7.370

7.519

7.524

7.532

7.537

7.544

7.550

7.612

7.618

7.622

7.632

7.642

7.645

7.648

7.851

7.858

7.862

7.864

7.872

7.875

7.877

7.889

7.900

7.912

9.059

14.95

4.00

2.00

1.00

3.00

2.00

1.00

NH

OPO

EtOEtO tBu

1H NMR spectrum of compound 3k

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.41

16.46

31.57

34.59

63.39

63.43

119.97

124.54

125.77

125.99

130.07

130.16

130.71

130.80

132.77

132.83

132.98

133.00

135.78

140.45

140.52

147.57

166.30

166.33

NH

OPO

EtOEtO tBu

13C NMR spectrum of compound 3k

S43

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

17.33

NH

OPO

EtOEtO tBu

31P NMR spectrum of compound 3k

10 9 8 7 6 5 4 3 2 1 0 ppm

1.288

1.300

1.311

3.804

4.132

4.144

4.155

4.157

4.168

4.169

4.179

4.181

6.880

6.885

6.889

6.897

6.901

6.906

7.528

7.530

7.533

7.536

7.540

7.543

7.546

7.548

7.553

7.555

7.559

7.561

7.633

7.638

7.641

7.646

7.649

7.653

7.659

7.661

7.664

7.872

7.875

7.877

7.884

7.886

7.890

5.99

3.00

4.00

2.00

1.00

2.99

1.99

1.00

NH

OPO

EtOEtO OMe

1H NMR spectrum of compound 3l

S44

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.45

16.50

55.70

63.44

63.48

114.38

121.83

124.56

125.80

130.12

130.21

130.81

130.90

131.73

132.71

132.77

133.03

133.04

140.44

140.50

156.71

166.15

166.19

NH

OPO

EtOEtO OMe

13C NMR spectrum of compound 3l

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

17.99

NH

OPO

EtOEtO OMe

31P NMR spectrum of compound 3l

S45

10 9 8 7 6 5 4 3 2 1 0 ppm

1.264

1.276

1.287

2.455

4.103

4.114

4.126

4.139

4.141

4.151

4.153

7.227

7.232

7.236

7.243

7.247

7.251

7.510

7.516

7.523

7.528

7.535

7.540

7.609

7.621

7.634

7.647

7.651

7.655

7.662

7.666

7.670

7.832

7.834

7.835

7.843

7.846

7.848

7.855

7.857

7.859

7.870

7.872

6.01

2.99

4.00

1.99

1.00

1.00

1.99

2.00

1.00

NH

OPO

EtOEtO SMe

1H NMR spectrum of compound 3m

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.39

16.43

16.77

63.41

63.45

120.69

124.54

125.78

128.05

130.17

130.26

130.71

130.80

132.61

132.67

132.95

132.97

133.80

136.13

140.16

140.23

166.27

166.30

NH

OPO

EtOEtO SMe

13C NMR spectrum of compound 3m

S46

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

17.79

NH

OPO

EtOEtO SMe

31P NMR spectrum of compound 3m

10 9 8 7 6 5 4 3 2 1 0 ppm

1.284

1.296

1.308

4.117

4.122

4.128

4.134

4.139

4.147

4.152

4.159

4.164

4.171

4.176

4.181

7.583

7.589

7.596

7.600

7.601

7.607

7.609

7.612

7.614

7.643

7.654

7.664

7.677

7.717

7.726

7.738

7.972

7.985

7.995

8.008

8.048

8.370

8.448

8.462

6.01

4.00

1.01

2.00

1.00

1.00

0.99

1.00

1.00

NH

OPO

EtOEtO

I

CF3

1H NMR spectrum of compound 3n

S47

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.53

16.57

63.20

63.24

89.76

120.36

122.16

122.30

123.97

125.61

125.77

126.57

126.59

126.85

127.81

128.03

128.25

128.48

128.99

129.07

130.54

130.63

132.97

132.99

133.64

133.70

136.17

136.19

136.22

139.76

139.82

141.80

167.30

167.33

NH

OPO

EtOEtO

I

CF3

13C NMR spectrum of compound 3n

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.56

NH

OPO

EtOEtO

I

CF3

31P NMR spectrum of compound 3n

S48

10 9 8 7 6 5 4 3 2 1 0 ppm

1.287

1.299

1.311

4.109

4.121

4.133

4.145

4.157

7.035

7.050

7.064

7.499

7.504

7.512

7.517

7.524

7.528

7.532

7.539

7.597

7.609

7.622

7.763

7.776

7.787

7.799

7.813

7.824

7.835

7.924

7.928

7.935

7.939

9.692

6.00

4.00

1.00

2.00

1.00

1.00

1.00

0.99

1.00

NH

OPO

EtOEtO F

Cl

1H NMR spectrum of compound 3o

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.41

16.45

63.46

63.51

116.56

116.71

119.82

119.86

121.05

121.17

122.25

124.67

125.91

130.31

130.40

130.69

130.78

132.60

132.65

132.91

132.92

135.31

135.33

139.80

139.87

154.08

155.71

166.41

166.44

NH

OPO

EtOEtO F

Cl

13C NMR spectrum of compound 3o

S49

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

17.64

NH

OPO

EtOEtO F

Cl

31P NMR spectrum of compound 3o

10 9 8 7 6 5 4 3 2 1 0 ppm

1.258

1.272

1.286

4.111

4.117

4.120

4.133

4.147

4.161

4.164

4.175

4.179

4.184

7.464

7.467

7.477

7.481

7.492

7.496

7.503

7.519

7.535

7.565

7.570

7.581

7.588

7.596

7.603

7.660

7.674

7.689

7.710

7.727

7.851

7.854

7.864

7.868

7.900

7.913

7.926

7.959

7.974

7.987

8.003

8.028

6.02

4.00

3.01

1.00

1.00

1.00

1.00

0.99

1.00

1.00

1.00

0.99

NH

OPO

EtOEtO

1H NMR spectrum of compound 3p

S50

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.39

16.44

63.35

63.39

120.40

121.39

124.60

125.93

126.01

126.08

126.16

126.42

127.32

128.76

130.15

130.26

130.43

130.53

132.97

133.06

133.13

134.32

140.47

140.55

167.34

167.37

NH

OPO

EtOEtO

13C NMR spectrum of compound 3p

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

17.87

NH

OPO

EtOEtO

31P NMR spectrum of compound 3p

S51

10 9 8 7 6 5 4 3 2 1 0 ppm

1.276

1.288

1.300

4.135

4.140

4.152

4.164

4.176

4.187

4.189

4.194

7.391

7.403

7.415

7.448

7.460

7.472

7.550

7.555

7.563

7.568

7.575

7.580

7.655

7.667

7.673

7.677

7.688

7.691

7.779

7.792

7.803

7.817

7.833

7.846

7.884

7.897

7.908

7.921

7.930

7.940

7.951

6.00

4.00

0.99

1.01

1.00

1.99

1.00

1.00

1.00

1.01

1.00

1.00

1.00

NH

OPO

EtOEtO

1H NMR spectrum of compound 3q

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.42

16.47

63.49

63.53

116.87

120.14

124.64

125.18

125.88

126.58

127.74

128.06

128.95

130.26

130.35

130.93

130.98

131.02

132.61

132.66

133.03

133.05

134.12

136.01

140.26

140.33

166.53

166.56

NH

OPO

EtOEtO

13C NMR spectrum of compound 3q

S52

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

18.02

NH

OPO

EtOEtO

31P NMR spectrum of compound 3q

10 9 8 7 6 5 4 3 2 1 0 ppm

1.252

1.264

1.276

4.104

4.113

4.116

4.129

4.141

4.153

4.157

4.164

4.169

6.995

7.003

7.007

7.014

7.015

7.020

7.547

7.551

7.552

7.560

7.563

7.565

7.572

7.576

7.578

7.609

7.621

7.634

7.706

7.709

7.722

7.732

7.735

7.975

7.988

7.999

8.011

8.120

8.126

8.128

8.136

8.145

6.01

4.00

0.99

1.00

1.00

2.00

1.00

1.00

0.99

1.00

NH

OPO

EtOEtO

N

1H NMR spectrum of compound 3r

S53

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.33

16.37

63.18

63.22

114.35

120.15

125.15

126.39

129.40

129.49

130.22

130.31

132.90

132.92

133.63

133.69

138.49

140.18

140.24

148.21

151.77

167.38

167.41

NH

OPO

EtOEtO

N

13C NMR spectrum of compound 3r

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.69

NH

OPO

EtOEtO

N

31P NMR spectrum of compound 3r

S54

10 9 8 7 6 5 4 3 2 1 0 ppm

1.164

1.176

1.188

3.967

3.979

3.991

4.005

4.017

5.860

5.876

7.114

7.130

7.131

7.148

7.174

7.178

7.185

7.189

7.192

7.199

7.203

7.304

7.318

7.329

7.339

7.526

7.528

7.531

7.533

7.539

7.540

7.544

7.546

7.551

7.553

7.557

7.559

7.609

7.611

7.622

7.632

7.635

7.677

7.686

7.687

7.698

7.936

6.00

4.00

1.00

1.00

0.98

4.01

1.00

1.00

0.98

1.00

0.97

PO

EtOEtO

NH

OPh

1H NMR spectrum of compound 3s

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.32

16.36

63.17

63.21

111.79

122.11

125.14

126.38

127.17

128.19

129.17

129.76

129.84

130.26

130.35

132.90

132.91

133.57

133.63

135.69

139.31

139.37

166.77

166.81

PO

EtOEtO

NH

OPh

13C NMR spectrum of compound 3s

S55

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.72

PO

EtOEtO

NH

OPh

31P NMR spectrum of compound 3s

10 9 8 7 6 5 4 3 2 1 0 ppm

1.303

1.317

1.331

3.970

4.161

4.175

4.189

4.203

4.206

4.217

4.220

7.136

7.151

7.165

7.347

7.363

7.378

7.722

7.738

7.959

7.969

7.975

7.985

8.274

8.290

8.516

8.518

8.545

8.548

9.266

6.01

3.00

4.00

1.00

2.00

2.01

1.00

1.00

0.99

0.99

NH

OPh

PO

EtOEtO

MeOOC

1H NMR spectrum of compound 3t

S56

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.43

16.48

52.89

63.81

63.86

120.26

124.95

125.32

126.82

129.30

131.23

131.34

131.66

131.77

133.78

133.80

133.83

133.91

138.24

143.98

144.07

165.50

165.54

165.70

165.71

NH

OPh

PO

EtOEtO

MeOOC

13C NMR spectrum of compound 3t

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.31

NH

OPh

PO

EtOEtO

MeOOC

31P NMR spectrum of compound 3t

S57

10 9 8 7 6 5 4 3 2 1 0 ppm

1.255

1.267

1.279

2.421

4.095

4.106

4.118

4.130

4.142

7.102

7.114

7.126

7.323

7.335

7.346

7.682

7.690

7.706

7.719

7.748

7.761

7.771

7.784

9.167

6.00

3.01

4.00

1.00

3.00

1.00

2.00

1.01

1.00

NH

OPh

PO

EtOEtO

Me

1H NMR spectrum of compound 3u

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.36

16.41

21.63

63.27

63.31

120.13

121.27

122.53

124.57

129.16

130.80

130.89

131.44

131.53

132.91

132.96

138.48

140.19

140.26

143.82

143.84

166.55

166.58

NH

OPh

PO

EtOEtO

Me

13C NMR spectrum of compound 3u

S58

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

18.60

NH

OPh

PO

EtOEtO

Me

31P NMR spectrum of compound 3u

10 9 8 7 6 5 4 3 2 1 0 ppm

1.254

1.266

1.278

3.869

4.081

4.086

4.089

4.093

4.098

4.101

4.110

4.113

4.122

4.126

4.134

4.138

4.143

7.006

7.010

7.014

7.020

7.024

7.029

7.107

7.120

7.132

7.326

7.339

7.352

7.397

7.402

7.405

7.409

7.713

7.726

7.791

7.805

7.814

7.828

9.277

6.01

3.00

4.00

1.00

1.00

1.99

1.00

2.00

1.00

1.00

NH

OPh

PO

EtOEtO

OMe

1H NMR spectrum of compound 3v

S59

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.38

16.42

55.81

63.19

63.24

115.75

115.92

116.02

116.06

116.16

117.03

120.16

124.64

129.17

134.96

135.02

138.43

142.31

142.39

163.04

163.07

166.05

166.08

NH

OPh

PO

EtOEtO

OMe

13C NMR spectrum of compound 3v

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

18.89

NH

OPh

PO

EtOEtO

OMe

31P NMR spectrum of compound 3v

S60

10 9 8 7 6 5 4 3 2 1 0 ppm

1.278

1.289

1.301

4.127

4.139

4.151

4.163

4.175

7.130

7.131

7.144

7.156

7.340

7.353

7.366

7.505

7.508

7.512

7.518

7.522

7.526

7.698

7.711

7.803

7.817

7.826

7.840

7.872

7.875

7.879

7.882

9.216

6.00

4.00

1.00

2.00

1.00

2.00

1.00

0.98

1.00

NH

OPh

PO

EtOEtO

Cl

1H NMR spectrum of compound 3w

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.40

16.44

63.61

63.65

120.21

123.13

124.39

124.89

129.24

130.25

130.34

131.03

131.12

134.23

134.29

138.20

139.65

139.68

141.88

141.96

164.90

164.93

NH

OPh

PO

EtOEtO

Cl

13C NMR spectrum of compound 3w

S61

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.90

NH

OPh

PO

EtOEtO

Cl

31P NMR spectrum of compound 3w

10 9 8 7 6 5 4 3 2 1 0 ppm

1.275

1.286

1.298

4.123

4.135

4.147

4.159

4.172

7.129

7.142

7.154

7.337

7.351

7.364

7.667

7.671

7.675

7.681

7.684

7.689

7.693

7.706

7.720

7.733

7.742

7.756

8.023

8.026

8.031

8.034

9.193

6.00

4.00

1.00

2.00

2.99

1.00

0.99

1.00

NH

OPh

PO

EtOEtO

Br

1H NMR spectrum of compound 3x

S62

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.41

16.45

63.65

63.69

120.22

123.59

124.85

124.92

128.12

128.14

129.26

133.28

133.38

133.89

133.98

134.21

134.28

138.18

141.80

141.88

164.80

164.83

NH

OPh

PO

EtOEtO

Br

13C NMR spectrum of compound 3x

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

17.03

NH

OPh

PO

EtOEtO

Br

31P NMR spectrum of compound 3x

S63

13 12 11 10 9 8 7 6 5 4 3 2 1 0 ppm

1.329

1.341

1.352

4.107

4.119

4.124

4.133

4.136

4.145

4.148

4.150

4.157

4.162

4.174

4.187

4.199

4.202

4.211

4.216

4.223

4.228

4.239

7.097

7.098

7.109

7.122

7.294

7.303

7.311

7.324

7.337

7.350

7.545

7.549

7.554

7.558

7.792

7.805

7.806

12.118

6.01

4.01

1.00

0.99

2.00

1.00

2.00

1.00

NH

OPh

PO

EtOEtO

S

1H NMR spectrum of compound 3y

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.38

16.42

63.45

63.49

120.28

124.45

124.70

125.94

129.10

130.35

130.48

132.71

132.79

138.77

151.41

151.54

158.70

158.73

NH

OPh

PO

EtOEtO

S

13C NMR spectrum of compound 3y

S64

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

14.03

NH

OPh

PO

EtOEtO

S

31P NMR spectrum of compound 3y

10 9 8 7 6 5 4 3 2 1 0 ppm

3.762

3.781

7.113

7.126

7.138

7.327

7.340

7.353

7.526

7.531

7.538

7.543

7.551

7.556

7.630

7.643

7.656

7.701

7.715

7.827

7.838

7.850

7.862

7.875

9.027

6.01

0.99

2.01

1.00

1.00

2.00

2.01

1.00

NH

OPh

PO

MeOMeO


S65

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

53.81

53.85

120.27

123.63

124.78

124.87

129.26

130.21

130.31

130.48

130.57

132.94

133.00

133.22

133.24

138.43

140.52

140.59

166.47

166.50

NH

OPh

PO

MeOMeO


-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

20.33

NH

OPh

PO

MeOMeO

31P NMR spectrum of compound 4a

S66

10 9 8 7 6 5 4 3 2 1 0 ppm

1.240

1.250

1.263

1.274

4.719

4.729

4.740

4.750

4.761

4.771

7.070

7.082

7.094

7.295

7.307

7.320

7.498

7.504

7.567

7.579

7.707

7.720

7.843

7.854

7.864

7.883

7.896

7.907

7.920

9.406

12.01

2.00

1.00

2.01

1.01

1.00

2.01

2.00

1.00

NH

OPh

PO

iPrO

iPrO


180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

23.88

23.91

24.09

24.11

72.33

72.37

120.06

124.40

125.79

127.04

129.01

129.98

130.08

130.87

130.96

132.54

132.60

138.47

140.04

140.11

166.30

166.33

NH

OPh

PO

iPrO

iPrO


S67

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

15.81

NH

OPh

PO

iPrO

iPrO

31P NMR spectrum of compound 4b

10 9 8 7 6 5 4 3 2 1 0 ppm

1.253

1.263

1.387

1.398

4.722

4.733

4.743

4.746

4.754

4.756

4.766

4.777

7.100

7.112

7.125

7.303

7.311

7.320

7.329

7.342

7.355

7.529

7.532

7.537

7.541

7.800

7.812

5.99

5.99

2.00

0.99

2.99

1.01

2.00

NH

OPO

iPrO

iPrO

Ph

S

1H NMR spectrum of compound 4c

S68

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

23.93

23.96

24.19

24.22

72.70

72.73

120.35

124.43

126.36

127.61

129.12

130.12

130.24

133.09

133.17

138.86

150.79

150.92

158.88

158.90

NH

OPO

iPrO

iPrO

Ph

S

13C NMR spectrum of compound 4c

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

11.53

NH

OPO

iPrO

iPrO

Ph

S

31P NMR spectrum of compound 4c

S69

10 9 8 7 6 5 4 3 2 1 0 ppm

0.826

0.828

1.258

1.270

1.283

1.295

1.308

1.320

1.561

1.565

1.573

1.576

1.584

1.587

1.589

1.595

1.598

1.609

4.031

4.033

4.036

4.042

4.044

4.047

4.049

4.053

4.055

4.059

4.061

4.066

4.070

4.073

7.081

7.093

7.105

7.298

7.300

7.312

7.324

7.326

7.499

7.511

7.523

7.589

7.601

7.614

7.709

7.723

7.826

7.840

7.850

7.862

9.284

6.03

4.00

4.02

4.04

1.01

2.01

1.01

1.02

2.01

2.01

1.00

NH

OPh

PO

nBuO

nBuO

1H NMR spectrum of compound 4d

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

13.62

18.77

32.44

32.48

67.07

67.11

120.04

124.49

124.57

125.81

129.05

130.08

130.17

130.73

130.82

132.51

132.57

132.86

138.49

140.21

140.28

166.28

166.31

NH

OPh

PO

nBuO

nBuO

13C NMR spectrum of compound 4d

S70

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

20.33

NH

OPh

PO

nBuO

nBuO

31P NMR spectrum of compound 4d

11 10 9 8 7 6 5 4 3 2 1 0 ppm

1.199

1.211

1.223

3.913

3.917

3.924

3.929

3.936

3.941

3.953

4.087

4.099

4.103

4.111

4.115

4.123

4.128

7.100

7.112

7.125

7.311

7.324

7.337

7.388

7.394

7.401

7.407

7.414

7.420

7.460

7.462

7.464

7.473

7.475

7.485

7.487

7.530

7.531

7.542

7.543

7.555

7.556

7.591

7.604

7.616

7.619

7.628

7.631

7.678

7.691

7.702

7.711

7.723

7.886

7.894

7.898

7.906

9.698

3.00

1.00

1.01

1.00

2.00

2.02

1.00

1.01

2.01

4.00

1.00

1.00

NH

OPh

PO

EtOPh

1H NMR spectrum of compound 4f

S71

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.39

16.44

62.13

62.17

120.03

124.48

128.30

128.78

128.85

128.94

129.10

129.21

129.67

130.05

130.13

131.17

131.24

132.05

132.12

132.45

132.53

132.78

132.80

133.16

133.18

138.50

140.52

140.58

166.18

166.21

NH

OPh

PO

EtOPh

13C NMR spectrum of compound 4f

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

35.66

NH

OPh

PO

EtOPh

31P NMR spectrum of compound 4f

S72

11 10 9 8 7 6 5 4 3 2 1 0 ppm6.695

6.704

6.712

7.063

7.075

7.088

7.284

7.298

7.311

7.478

7.483

7.486

7.490

7.495

7.503

7.508

7.577

7.579

7.589

7.591

7.602

7.604

7.638

7.640

7.652

7.659

7.661

7.673

7.765

7.778

1.00

1.00

2.01

5.01

2.01

4.02

2.00

NH

OPO

PhPh

Ph

S

1H NMR spectrum of compound 4g

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

120.41

124.37

129.02

129.11

129.19

129.27

129.81

129.92

131.05

131.78

131.94

132.02

133.07

133.09

133.49

133.60

138.93

152.59

152.66

159.11

NH

OPO

PhPh

Ph

S

13C NMR spectrum of compound 4g

S73

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

29.27

NH

OPO

PhPh

Ph

S

31P NMR spectrum of compound 4g

11 10 9 8 7 6 5 4 3 2 1 0 ppm

7.013

7.025

7.038

7.100

7.114

7.124

7.137

7.190

7.202

7.214

7.395

7.407

7.428

7.440

7.487

7.499

7.512

7.629

7.641

7.648

7.661

7.682

8.062

8.068

8.075

8.080

10.536

1.00

0.99

2.01

7.00

2.01

5.01

1.00

1.00

NH

OPh

PO

PhPh

1H NMR spectrum of compound 4h

S74

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

120.12

124.14

128.54

128.68

128.76

129.32

129.97

130.12

130.20

130.82

131.55

131.61

132.24

132.30

132.42

132.83

133.21

133.28

137.90

141.32

141.37

165.42

NH

OPh

PO

PhPh

13C NMR spectrum of compound 4h

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

35.45

NH

OPh

PO

PhPh

31P NMR spectrum of compound 4h

S75

11 10 9 8 7 6 5 4 3 2 1 0 ppm

7.106

7.119

7.130

7.142

7.164

7.169

7.172

7.180

7.184

7.188

7.403

7.409

7.416

7.422

7.429

7.433

7.436

7.441

7.444

7.447

7.453

7.457

7.508

7.510

7.512

7.520

7.523

7.533

7.535

7.537

7.623

7.625

7.637

7.644

7.646

7.657

7.668

7.671

7.673

7.681

7.684

7.686

7.694

7.696

1.02

1.99

7.00

1.99

4.01

1.04

1.00

0.99

O

NH

POPh

PhCl

1H NMR spectrum of compound 4i

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

121.45

128.71

128.90

128.98

129.14

129.43

130.09

130.46

130.54

130.80

131.68

131.75

132.44

132.50

132.70

132.72

133.03

133.04

133.42

133.50

136.76

141.10

141.16

165.58

165.60

O

NH

POPh

PhCl

13C NMR spectrum of compound 4i

S76

-60-50-40-30-20-10110 100 90 80 70 60 50 40 30 20 10 0 ppm

35.84

O

NH

POPh

PhCl

31P NMR spectrum of compound 4i

10 9 8 7 6 5 4 3 2 1 0 ppm

1.254

2.353

6.955

6.968

7.224

7.237

7.250

7.409

7.423

7.448

7.460

7.473

7.509

7.519

7.531

7.542

7.851

7.863

7.897

12.01

3.00

1.00

1.02

1.00

1.99

1.02

2.01

0.99

NH

O

Bpin

Me


S77

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

21.72

25.23

83.73

117.52

121.10

125.58

127.24

128.96

129.10

131.98

135.29

138.08

139.22

165.96

NH

O

Bpin

Me


12 11 10 9 8 7 6 5 4 3 2 1 0 ppm

1.452

7.112

7.114

7.116

7.125

7.126

7.129

7.137

7.140

7.141

7.351

7.354

7.358

7.367

7.369

7.372

7.378

7.381

7.384

7.505

7.711

7.715

7.717

7.720

7.726

7.730

7.731

10.752

11.98

0.99

2.00

1.98

1.99

1.00

NH

OPh

Bpin

S


S78

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

25.14

85.60

119.95

124.23

129.25

130.09

136.39

139.09

151.92

160.51

NH

OPh

Bpin

S


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