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Transcript of DQGWKH&HQWUH1DWLRQDOGHOD5HFKHUFKH6FLHQWLILTXH · Martín Camacho-Espinoza, Alberto Reyes-Deloso, R....
Supporting Information
Thiazole-based non-symmetric NNC-Palladium pincer complexes as catalytic precursors for the Suzuki–Miyaura C-C coupling
Martín Camacho-Espinoza, Alberto Reyes-Deloso, R. Alfredo Toscano, J. Guillermo Penieres-Carrillo, José G. López-Cortés, M. Carmen Ortega-Alfaro, and Fernando Ortega-Jiménez.
CONTENTS
i. FT-IR, MS and NMR spectra of ligand 1a-c S1
ii. FT-IR, MS and NMR spectra of palladadium complexes 2a-c S19
iii. Spectroscopic data of coupling products S37
iii. NMR spectra of coupling products S40
iii. References S60
Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019
S1
FT-IR compound 1a
MS-DART compound 1a
N
S NN
N
S NN
S2
1H NMR (300 MHz, CDCl3) compound 1a
13C NMR (75 MHz, CDCl3) compound 1a
N
S NN
N
S NN
S3
FT-IR compound 1b
MS-DART compound 1b
N
S NN
N
S NN
S4
1H NMR (300 MHz, CDCl3) compound 1b
13C NMR (75 MHz, CDCl3) compound 1b
N
S NN
N
S NN
S5
FT-IR compound 1c
MS-DART compound 1c
N
S NN
Ph
N
S NN
Ph
S6
1H NMR (300 MHz, CDCl3) compound 1c
13C NMR (75 MHz, CDCl3) compound 1c
N
S NN
Ph
N
S NN
Ph
S7
FT-IR compound 1d
MS-DART compound 1d
N
S NN
N
S NN
S8
1H NMR (300 MHz, CDCl3) compound 1d
13C NMR (75 MHz, CDCl3) compound 1d
N
S NN
N
S NN
S9
FT-IR compound 1e
MS-EI compound 1e
N
S NN
N
S NN
S10
1H NMR (300 MHz, CDCl3) compound 1e
13C NMR (75 MHz, CDCl3) compound 1e
N
S NN
N
S NN
S11
FT-IR compound 1f
MS-DART compound 1f
N
S NN
Ph
N
S NN
Ph
S12
1H NMR (300 MHz, CDCl3) compound 1f
13C NMR (75 MHz, CDCl3) compound 1f
N
S NN
Ph
N
S NN
Ph
S13
FT-IR compound 1g
MS-EI compound 1g
N
S NN
H3C
N
S NN
H3C
S14
1H NMR (300 MHz, CDCl3) compound 1g
13C NMR (75 MHz, CDCl3) compound 1g
N
S NN
H3C
N
S NN
H3C
S15
FT-IR compound 1h
MS-DART compound 1h
N
S NN
H3C
CH3
N
S NN
H3C
CH3
S16
1H NMR (300 MHz, CDCl3) compound 1h
13C NMR (75 MHz, CDCl3) compound 1h
N
S NN
H3C
CH3
N
S NN
H3C
CH3
N
S NN
H3C
CH3
S17
FT-IR compound 1i
MS-DART compound 1i
N
S NN
H3C
N
S NN
H3C
S18
1H NMR (300 MHz, CDCl3) compound 1i
13C NMR (75 MHz, CDCl3) compound 1i
N
S NN
H3C
N
S NN
H3C
S19
FT-IR compound 2a
MS-FAB+ compound 2a
N
S NN
PdCl
N
S NN
PdCl
S20
1H NMR (500 MHz, CD2Cl2) compound 2a
13C NMR (125 MHz, CD2Cl2) compound 2a
N
S NN
PdCl
N
S NN
PdCl
S21
FT-IR compound 2b
MS-FAB+ compound 2b
N
S NN
PdCl
N
S NN
PdCl
S22
1H NMR (300 MHz, DMSO-d6) compound 2b
13C NMR (75 MHz, DMSO-d6) compound 2b
N
S NN
PdCl
N
S NN
PdCl
S23
FT-IR compound 2c
MS-FAB+ compound 2c
N
S NN
PdCl
Ph
N
S NN
PdCl
Ph
S24
1H NMR (500 MHz, CD2Cl2) compound 2c
13C NMR (125 MHz, CD2Cl2) compound 2c
N
S NN
PdCl
Ph
N
S NN
PdCl
Ph
S25
FT-IR compound 2d
MS-FAB+ compound 2d
N
S NN
PdCl
N
S NN
PdCl
S26
1H NMR (500 MHz, CD2Cl2) compound 2d
13C NMR (125 MHz, CD2Cl2) compound 2d
N
S NN
PdCl
N
S NN
PdCl
S27
FT-IR compound 2e
MS-FAB+ compound 2e
N
S NN
PdCl
N
S NN
PdCl
S28
1H NMR (300 MHz, DMSO-d6) compound 2e
13C NMR (75 MHz, DMSO-d6) compound 2e
N
S NN
PdCl
N
S NN
PdCl
S29
FT-IR compound 2f
MS-FAB+ compound 2f
N
S NN
PdCl
Ph
N
S NN
PdCl
Ph
S30
1H NMR (500 MHz, CD2Cl2) compound 2f
13C NMR (125 MHz, CD2Cl2) compound 2f
N
S NN
PdCl
Ph
N
S NN
PdCl
Ph
S31
FT-IR compound 2g
MS-FAB+ compound 2g
N
S NN
H3CPdCl
N
S NN
H3CPdCl
S32
1H NMR (300 MHz, DMSO-d6) compound 2g
13C NMR (75 MHz, DMSO-d6) compound 2g
N
S NN
H3CPdCl
N
S NN
H3CPdCl
S33
FT-IR compound 2h
MS-FAB+ compound 2h
N
S NN
H3C
CH3
PdCl
N
S NN
H3C
CH3
PdCl
S34
1H NMR (300 MHz, DMSO-d6) compound 2h
13C NMR (75 MHz, DMSO-d6) compound 2h
N
S NN
H3C
CH3
PdCl
N
S NN
H3C
CH3
PdCl
S35
FT-IR compound 2i
MS-FAB+ compound 2i
N
S NN
H3CPdCl
N
S NN
H3CPdCl
S36
1H NMR (300 MHz, DMSO-d6) compound 2i
13C NMR (75 MHz, DMSO-d6) compound 2i
N
S NN
H3CPdCl
N
S NN
H3CPdCl
S37
4-Methoxybiphenyl 5a.1 White solid. mp 88-90 °C. 1H-NMR (300 MHz, CDCl3) : 3.85 (s,
3H, OCH3), 6.98 (d, J = 8.0 Hz, 2H, Ar), 7.30 (t, J = 7.6 Hz, 1H, Ar); 7.42 (t, J = 7.5 Hz, 2H,
Ar), 7.50-7.57 (m, 4H, Ar). 13-CNMR (75 MHz, CDCl3) : 55.3, 114.1, 126.6, 126.7, 128.1,
128.7, 133.7, 140.8, 159.1.
4-Methylbiphenyl 5b.1 White solid. mp 45-47 °C. 1H-NMR (300 MHz, CDCl3) : 2.39 (s,
3H, CH3), 7.26 (d, J = 7.8 Hz, 2H, Ar), 7.31(t, J = 7.8 Hz, 1H, Ar), 7.42 (t, J = 7.8 Hz, 2H,
Ar), 7.50 (d, J = 8.4 Hz, 2H, Ar), 7.59 (d, J = 7.8 Hz, 2H, Ar). 13-CNMR (75 MHz, CDCl3)
:21.0, 126.9, 128.6, 129.4, 136.9, 138.3, 141.1.
3-Methylbiphenyl 5c.2 Colorless oil. 1H-NMR (300 MHz, CDCl3) : 2.59 (s, 3H, CH3), 7.35
(d, J = 7.5 Hz, 1H, Ar), 7.50 (t, J = 7.5 Hz, 2H, Ar), 7.60 (t, J = 7.5 Hz, 4H, Ar), 7.76 (d, J =
7.5 Hz, 2H, Ar). 13-CNMR (75 MHz, CDCl3) : 21.4, 124.2, 127.1, 127.9, 128.6, 13802.
141.1, 141.3
2-Methylbiphenyl 5d.1 Colorless oil. 1H-NMR (300 MHz, CDCl3) : 2.58 (s, 3H, CH3), 7.54-
7.68 (m, 9H, Ar),. 13-CNMR (75 MHz, CDCl3) : 20.3, 125.7,126.6, 127.1, 127.9, 129.1,
129.7, 130.2, 135.1, 141.9.
1-phenylnaphthalene 5e.1 Colourless oil. 1H-NMR (300 MHz, CDCl3) : 7.38 (d, J = 7.2 Hz,
1H, Ar), 7.51-7.46 (m, 4H, Ar), 7.76-7.72 (m, 3H, Ar), 7.93-7.85 (m, 3H, Ar), 8.05 (s, 1H,
Ar). 13-CNMR (75 MHz, CDCl3) : 123.1, 124.7, 125.9, 127.1, 127.4, 127.9, 128.7, 128.8,
132.1, 134.4, 140.0, 142.4.
2,6-dimethylbiphenyl 5f.3 Colourless oil. 1H-NMR (300 MHz, CDCl3) : 2.0 (s, 6H, CH3),
7.11-7.17 (m, 4H, Ar), 7.35 (t, J = 6.6 Hz, 1H, Ar), 7.42 (t, J = 6.6 Hz, 1H, Ar), 7.42 (d, J =
6.6 Hz, 2H, Ar). 13-CNMR (75 MHz, CDCl3) : 20.8, 126.5, 126.9, 127.1, 127.2, 128.3,
128.7, 129.0, 136.0, 141.0, 141.8.
Biphenyl 5g.1 White solid. mp 68-70°C. 1H-NMR (300 MHz, CDCl3) : 7.34 (t, J = 7.2 Hz,
2H, Ar). 7.44 (t, J = 7.2 Hz, 4H, Ar), 7.61 (d, J = 7.2 Hz, 4H, Ar). 13-CNMR (75 MHz,
CDCl3) : 127.1. 127.2, 128.7, 141.2.
S38
4-Nitrobiphenyl 5h.1 Yellow solid. mp 112-114 °C. 1H-NMR (300 MHz, CDCl3) : 7.44-7.52
(m, 3H, Ar), 7.63 (d, J = 8.1 Hz, 2H, Ar), 7.75 (d, J = 9.3 Hz, 2H, Ar), 8.31 (d, J = 8.4 Hz,
2H, Ar). 13-CNMR (75 MHz, CDCl3) : 124.0, 127.3, 127.7, 128.8, 129.1, 138.7, 147.0,
147.5.
4-Acetylbiphenyl 5i.1 White solid. mp 120-121°C. 1H-NMR (300 MHz, CDCl3) : 2.64 (s,
3H, CH3), 7.40 (d, J = 7.6 Hz, 1H, Ar), 7.47 (t, J = 7.6 Hz, 2H, Ar), 7.62 (d, J = 7.6 Hz, 2H,
Ar), 7.70 (d, J = 8.0 Hz, 2H, Ar), 8.05 (d, J = 8.0 Hz, 2H, Ar). CNMR (75 MHz, CDCl3) :
197.9, 145.7, 139.8, 135.8, 128.9, 128.2, 127.3 127.2, 26.6.
2-phenylpyridine 5j.4 Colourless oil. 1H-NMR (300 MHz, CDCl3) : 7.32-7.59 (m, 6H, Ar),
7.87 (d, J = 7.2 Hz 1H, Ar), 8.59 (d, J = 6.3 Hz 1H, Ar), 8.85 (d, J = 4.8 Hz, 1H, Ar). 13-
CNMR (75 MHz, CDCl3) : 123.4, 127.0, 128.0, 128.7, 128.9, 130.7, 134.2, 136.5, 137.7,
148.2, 148.3.
3-phenylpyridine 5k.5 Colourless oil. 1H-NMR (300 MHz, CDCl3) : 7.34-7.37 (m, 3H, Ar),
7.44 (t, J = 7.8 Hz 2H, Ar), 7.58 (d, J = 7.2 Hz 2H, Ar), 8.62 (d, J = 4.8 Hz, 2H, Ar). 13-
CNMR (75 MHz, CDCl3) : 121.2, 127.1, 127.2, 128.7, 141.2, 150.1, 152.1.
2-phenylthiophene 5l.4 Colourless oil. 1H-NMR (300 MHz, CDCl3) : 7.06-7.09 (m, 1H, Ar),
7.25-7.44 (m, 5H, Ar), 7.60-7.63 (m, 2H, Ar). 13-CNMR (75 MHz, CDCl3) : 123.0, 124.7,
125.9, 127.1, 127.4, 127.9, 128.7, 128.8.
3-phenylthiophene 5m.6 Colourless oil. 1H-NMR (300 MHz, CDCl3) : 7.29-7.47 (m, 6H,
Ar), 7.61 (d, J = 9.6 Hz, 2H, Ar).13-CNMR (75 MHz, CDCl3) : 119.7, 120.2, 126.1, 126.3,
126.4, 127.1, 128.7.
4-methoxy-4'-methylbiphenyl 5n.5 White solid. mp 112-114 °C. 1H-NMR (300 MHz, CDCl3)
: 2.38 (s, 3H, CH3), 3.84 (s, 3H, OCH3), 6.98 (d, J = 8.7 Hz, 2H, Ar), 7.24 (d, J = 7.8 Hz,
2H, Ar), 7.46 (d, J = 7.8 Hz, 2H, Ar), 7.52 (d, J = 8.7 Hz, 2H, Ar). 13-CNMR (75 MHz,
CDCl3) : 21.0, 55.3, 114.1, 126.5, 127.9, 128.7, 129.4, 130.8, 133.7, 136.3, 137.9, 158.8.
4,4'-dimethoxybiphenyl 5o.7 White solid. mp 178-180 °C. 1H-NMR (300 MHz, CDCl3) :
3.84 (s, 6H, OCH3), 6.97 (d, J = 9.0 Hz, 4H, Ar), 7.45 (d, J = 9.0 Hz, 4H, Ar). 13-CNMR (75
MHz, CDCl3) : 55.3, 114.1, 127.7, 133.4, 158.6.
S39
4-methoxy-4'-nitrobiphenyl 5p.5 White solid. mp 106-108 °C. 1H-NMR (300 MHz, CDCl3)
: 3.87 (s, 3H, OCH3), 7.03 (d, J = 9.0 Hz, 2H, Ar), 7.59 (d, J = 9.0 Hz, 2H, Ar), 7.70 (d, J =
8.7 Hz, 2H, Ar), 8.28 (d, J = 9.0 Hz, 2H, Ar). 13-CNMR (75 MHz, CDCl3) : 55.3, 114.5,
124.1, 127.0, 128.5, 131.0, 146.4, 147.1, 160.3.
4-methoxy-4'-(trifluoromethyl)biphenyl 5q.8 White solid. mp 124-126 °C. 1H-NMR (300
MHz, CDCl3) : 3.86 (s, 3H, OCH3), 7.02 (d, J = 9.0 Hz, 2H, Ar), 7.56 (d, J = 9.0 Hz, 2H,
Ar), 7.65 (s, 4H, Ar). 13-CNMR (75 MHz, CDCl3) : 55.3, 114.4, 122.5, 125.6, 126.1, 126.8,
128.3, 128.8, 130.8, 132.1, 144.2, 159.8.
4-methyl-‘4-nitro-biphenyl 5r.8 White solid. mp 132-134 °C. 1H-NMR (300 MHz, CDCl3) :
2.42 (s, 3H, Me). 7.31 (d, J = 7.8 Hz, 2H, Ar), 7.54 (d, J = 8.4 Hz, 2H, Ar),7.73 (d, J = 9.0
Hz, 2H, Ar) 8.29 (d, J = 9.0 Hz, 2H, Ar), 13-CNMR (75 MHz, CDCl3) : 21.1, 124.0, 127.1,
127.4, 129.8, 135.8, 139.0, 146.8, 147.5.
4-nitro-4'-(trifluoromethyl)biphenyl 5s.9 White solid. mp 108-110 °C. 1H-NMR (300 MHz,
CDCl3) : 7.75-7.78 (m, 6H, Ar), 8.36 (d, J = 8.70 Hz, 2H, Ar). 13-CNMR (75 MHz, CDCl3)
: 124.3, 126.1, 127.7, 128.1, 128.8, 130.8, 146.0, 147.6.
4,4’-dinitro-4'-biphenyl 5t.9 White solid. mp 240-242 °C. 1H-NMR (300 MHz, CDCl3) :
7.81 (d, J = 9.3 Hz, 4H, Ar), 8.38 (d, J = 9.0 Hz, 4H, Ar). 13-CNMR (75 MHz, CDCl3) :
124.4, 128.3, 144.9, 148.0.
S40
1H NMR (300 MHz, CDCl3) compound 5a
13C NMR (75 MHz, CDCl3) compound 5a
H3CO
H3CO
S41
1H NMR (300 MHz, CDCl3) compound 5b
13C NMR (75 MHz, CDCl3) compound 5b
H3C
H3C
S42
1H NMR (300 MHz, CDCl3) compound 5c
13C NMR (75 MHz, CDCl3) compound 5c
CH3
CH3
S43
1H NMR (300 MHz, CDCl3) compound 5d
13C NMR (75 MHz, CDCl3) compound 5d
H3C
H3C
S44
1H NMR (300 MHz, CDCl3) compound 5e
13C NMR (75 MHz, CDCl3) compound 5e
S45
1H NMR (300 MHz, CDCl3) compound 5f
13C NMR (75 MHz, CDCl3) compound 5f
H3C
CH3
H3C
CH3
S46
1H NMR (300 MHz, CDCl3) compound 5g
13C NMR (75 MHz, CDCl3) compound 5g
S47
1H NMR (300 MHz, CDCl3) compound 5h
13C NMR (75 MHz, CDCl3) compound 5h
O2N
O2N
S48
1H NMR (300 MHz, CDCl3) compound 5i
13C NMR (75 MHz, CDCl3) compound 51
H3C
O
H3C
O
S49
1H NMR (300 MHz, CDCl3) compound 5j
13C NMR (75 MHz, CDCl3) compound 5j
N
N
S50
1H NMR (300 MHz, CDCl3) compound 5k
13C NMR (75 MHz, CDCl3) compound 5k
N
N
S51
1H NMR (300 MHz, CDCl3) compound 5l
13C NMR (75 MHz, CDCl3) compound 5l
S
S
S52
1H NMR (300 MHz, CDCl3) compound 5m
13C NMR (75 MHz, CDCl3) compound 5m
S
S
S53
1H NMR (300 MHz, CDCl3) compound 5n
13C NMR (75 MHz, CDCl3) compound 5n
H3CO
CH3
H3CO
CH3
S54
1H NMR (300 MHz, CDCl3) compound 5o
13C NMR (75 MHz, CDCl3) compound 5o
H3CO
OCH3
H3CO
OCH3
S55
1H NMR (300 MHz, CDCl3) compound 5p
13C NMR (75 MHz, CDCl3) compound 5p
H3CO
NO2
H3CO
NO2
S56
1H NMR (300 MHz, CDCl3) compound 5q
13C NMR (75 MHz, CDCl3) compound 5q
H3CO
CF3
H3CO
CF3
S57
1H NMR (300 MHz, CDCl3) compound 5r
13C NMR (75 MHz, CDCl3) compound 5r
O2N
Me
O2N
Me
S58
1H NMR (300 MHz, CDCl3) compound 5s
13C NMR (75 MHz, CDCl3) compound 5s
O2N
CF3
O2N
CF3
S59
1H NMR (300 MHz, CDCl3) compound 5t
13C NMR (75 MHz, CDCl3) compound 5t
O2N
NO2
O2N
NO2
S60
1. L. Bai, J-X. Wang, Adv. Synth. Catal. 2008, 350, 315–320.
2. X. Li, W. Che, H. Chang, Z. Shao, W. Wei, Synthesis 2014, 46, 1593–1602.
3. J. A. Weeden, R. Huang, K. D. Galloway, P. W. Gingrich, B. J. Frost, Molecules,
2011, 16, 6215–6231.
4. H. Liu, H. Liu, R. Li, H. Chen, Tetrahedron Lett. 2014, 55, 415–418.
5. B. B. A. Tairai, P. K. Bhattacharyya, P. Das, Appl. Organometal. Chem. 2016,
30, 519–523.
6. V. Ramakrishna, N. D. Reddy, Dalton Trans. 2017, 46, 8598–8610.
7. K. R. Balinge, A. G. Khiratkar, P. R. Bhagat, J. Organomet. Chem. 2018, 854,
131-139.
8. C. B. Baltus, N. J. Press, M. D. Antonijevic, G. J. Tizzard, S. J. Coles, J. Spencer,
Tetrahedron 2012, 45, 9272-9277.
9. J. Song, H. Zhao, Y. Liu, H. Han, Z. Li, W. Chu, Z. Sun, New J. Chem. 2017, 41,
372–376.