synthesis of biphenyl-based arsine ligands by suzuki

Synthesis of Biphenyl-Based Arsine Ligands by Suzuki-Miyaura Coupling and their Application to Pd-Catalyzed Arsination

Paula M. Uberman, Mario N. Lanteri, Sol C. Parajón Puenzo and Sandra E. Martín*

INFIQC, Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Nacional

de Córdoba, 5000, Córdoba, Argentina

Supplementary Material Contents 1. Experimental Section 1.1 General Methods 1

1.2 General Procedure for the preparation of n-Bu3SnAsPh2 2

1.3 Representative Procedure for Pd-Catalyzed Cross-Coupling Suzuki-

Miyaura Reaction 2

1.4 Representative Procedure for Pd-Catalyzed Arsination Reaction

with n-Bu3SnAsPh2 and Perfluoroalkyl Iodides (RfI) 2

2. Characterizations Data 3

3. NMR Spectroscopy 6

4. References 35

1. Experimental Section 1.1 General Methods

Gas chromatographic analyses were performed on a gas chromatograph with a flame

ionization detector, and equipped with the following columns: HP-1 25 m x 0.20 mm x 0.25 μm

column. 1H NMR, 13C NMR and 19F NMR were conducted on a High Resolution Spectrometer Bruker

Advance 400, in CDCl3 as solvent. Gas Chromatographic/Mass Spectrometer analysis were carried

out on a GC/MS QP 5050 spectrometer equipped with a VF-5ms, 30 m x 0.25 mm x 0.25 μm column.

Melting points were performed with an electrical instrument. The HRMS were recorded at the UCR

Mass Spectrometry Facility, University of California, USA. The Elemental Analyses were carried out on

an EXETER CE 440 at the UMYMFOR – FCEN, University of Buenos Aires, Argentina.

The AsPh3, PPh3, (o-bph)PCy2, (o-bph)PtBu2, PCy3, n-Bu3SnCl, (PPh3)2PdCl2, Pd(OAc)2,

Pd(dba)2, CuI, RfI, ArB(OH)2, K3PO4, Cs2CO3, Ba(OH)2, NaOH, Na2SO4 and ArI were commercially

available and used as received. (2-bromophenyl)diphenylarsine (2) was prepared as previously

reported from the corresponding 2-bromoiodobenzene.1 CsF was dried under vacuum at 120°C. All

solvents were analytical grade and distillated before use. Toluene was distilled under nitrogen with Na-

benzophenone and dioxane was distilled under nitrogen. All reactions were carried out under

atmosphere of nitrogen. Silica gel (0.063-0.200 mm) was used in column chromatography.

Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2011

2

1.2 General Procedure for the preparation of n-Bu3SnAsPh2. A typical procedure involves

the formation of Ph2As- ions from Ph3As and Na metal in liquid ammonia, followed by addition of n-

Bu3SnCl to obtain the n-Bu3SnAsPh2. Into a three-necked, 500 mL, round-bottomed flask equipped

with a cold finger condenser charged with dry ice-ethanol, a nitrogen inlet, and a magnetic stirrer,

approximately 400 mL of ammonia previously dried with Na metal under nitrogen was condensed.

AsPh3 (1.0 mmol) and then 2 equivalents of Na metal (2 mmol) in small pieces were added, with a

pause for bleaching between each addition. At 20-30 min of the last addition, Ph2As- anion was formed

(clear orange-red solution), and n-Bu3SnCl (1 mmol) was added slowly. The mixture was then stirred

for 5 min and the liquid ammonia allowed to evaporate. The evaporation left a white solid residue

which was dissolved in dry organic solvent (12 mL). Reagent 1 was formed in almost quantitative

yield. This stannane solution without purification was used for the cross-coupling Pd-catalyzed

arsinations.

1.3 Representative Procedure for Pd-Catalyzed Cross-Coupling Suzuki-Miyaura Reaction. The following procedure of the reaction is representative of all cross-coupling Suzuki-

Miyaura reactions. Into a 25 mL Schlenk tube with Teflon screw-cap septum equipped with a magnetic

stirrer and a nitrogen inlet, Pd(OAc)2 (1 mol%, 0.01 mmol), PPh3 (Pd:L 1:4, 0.04 mmol) (2-

bromophenyl)diphenylarsine (2) (1 mmol), arylboronic acid (3a-g) (1.5 mmol), K3PO4 (2 mmol) were

added, and then dioxane (5 mL) and water (2.5 mL) were added. The reaction mixture was heated for

24 h in an oil bath at 100°C. The solvent condensation took place on the walls of Schlenk tube. After

being cooled to room temperature, the mixture was open to the air and diluted with water and then

extracted three times with CH2Cl2 (30 mL each). The biarylarsine product was purified in an open

atmosphere by silica-gel column chromatography after being dried with anhydrous Na2SO4. These

reactions were scaled up to 5 mmol of (2-bromophenyl)diphenylarsine (2) at most.

1.4 Representative Procedure for Pd-Catalyzed Arsination Reaction with n-Bu3SnAsPh2 and Perfluoroalkyl Iodides (RfI). The following procedure of the reaction of n-Bu3SnAsPh2 (1) with

perfluorooctyl iodide (4a) is representative of all these reactions. Into a three-necked, 500-mL, round-

bottomed flask equipped with a cold finger condenser charged with dry ice-ethanol, a nitrogen inlet,

and a magnetic stirrer, approximately 400 mL of ammonia previously dried with Na metal under

nitrogen was condensed. The AsPh3 (1.0 mmol) was added followed by 2 equivalents of Na metal (2

mmol) in small pieces, waiting for bleaching between each addition. After 20-30 min of the last

addition, Ph2As- anion was formed (clear orange-red solution), and n-Bu3SnCl (1 mmol) was added

slowly. The mixture was stirred for 5 min and the liquid ammonia was then allowed to evaporate.

Evaporation left a solid white residue which was dissolved in dry toluene (12 mL). This solution was

added via cannula and syringe into a Schlenk tube. In the tube, CsF (3 eq.) was previously dried

under vacuum at 120°C for 3 h; after cooling the tube at room temperature, (PPh3)2PdCl2 (10 mol%),

ligand (40 mol%), substrate 4a (0.7 mmol) and toluene (3 mL) were added. When the solution of

stannane 1 was added, the reaction mixture turned deep brown. The reaction mixture was heated for

24 h in an oil bath at reflux. Water was added to the cooled reaction mixture and then extracted three


3

times with CH2Cl2 (30 mL each). After being dried with anhydrous Na2SO4, product 5 was quantified by

CG using the internal standard method.

The products were characterized by 1H NMR, 13C NMR, GC-MS and HRMS. All these

spectroscopic data agreed with those previously reported for compounds L11 and 5-8.2

2. Characterizations Data

2-Diphenylarsino-2’-methylbiphenyl (L2). Compound L2 was obtained according to

the general procedure. Product L2 was isolated from the reaction mixture by silica-gel

column chromatography (petroleum ether) obtaining 0.3488 g of L2 (88 % yield). After

crystallization from CH3CN cubic crystals were obtained (mp 74.3-75.7 °C). 1H-NMR

(CDCl3): δ 7.42-7.18 (16 H, m); 7.08-7.04 (1 H, m); 6.91 (1 H, d, 3J = 8 Hz); 2.05 (3 H, s). 13C-NMR

(CDCl3): δ 147.45; 141.61; 139.95; 139.90; 139.69; 136.03; 134.00; 133.94; 133.84; 130.43; 129.80;

129.62; 128.51; 127.74; 127.57; 125.05; 20.51. NMR 2D (COSY-45) δH /δH: 2.05 / 6.91; 2.05 / 7.09;

2.05 / 7.23; 6.91 / 7.09; 6.91 / 7.26. NMR 2D (HSQC) δH /δC: 2.05 / 20.51; 6.90 /129.80; 7.04 / 125.05;

7.23 / 133.78; 7.38 / 128.51. MS: m/z (%): 396 (89), 381 (74), 303 (12), 241 (84), 227 (100), 165 (88),

152 (50), 139 (6), 115 (6), 91 (8), 78 (9), 51 (6). HRMS (EI): calcd. for C25H22As 397.0932, found

[M+H]+ 397.0937. Elemental Analysis (%) calc. for C25H21As: C, 75.76; H, 5.34; As, 18.90. Found: C,

75.53; H, 5.28.

2-Diphenylarsino-2’,6’-dimethylbiphenyl (L3). Compound L3 was obtained

according to the general procedure. Product L3 was isolated from the reaction

mixture by silica-gel column chromatography (petroleum ether), yielding 0.2914 g of

the product (71 % yield). After crystallization from CH3CN cubic crystals were

obtained (mp 92.5-93.3 °C). 1H-NMR (CDCl3): δ 7.40-7.37 (1 H, m); 7.29-7.17 (13 H, m); 7.10 (1 H, d, 3J = 7.6 Hz); 7.03 (2 H, d, 3J = 7.6 Hz); 1.79 (6 H, s). 13C-NMR (CDCl3): δ 146.60; 141.35; 139.89;

139.72; 136.39; 134.27; 133.80; 129.22; 129.05; 128.50; 128.22; 127.51; 127.34; 127.10; 20.77. NMR

2D (COSY-45) δH /δH: 1 / 6.82; 7.04 / 7.19; 7.11 / 7.40; 7.29 / 7.40. NMR 2D (HSQC) δH /δC: 1.79 /

20.77; 7.03 / 127.10; 7.10 / 129.22; 7.19 / 127.47; 7.24 / 133.76; 7.38 / 129.05. NMR 2D (HMBC) δH

/δC: 1.79 / 127.10; 1.79 / 136.39; 1.79 / 141.35; 7.04 / 20.77. MS: m/z (%): 410 (77), 395 (60), 317 (8),

255 (31), 241 (100), 227 (17), 179 (37), 165 (64), 152 (32), 91 (14), 77 (14), 51 (12). HRMS (EI): calcd. for C26H24As 411.1088, found [M-H]+ 411.1099. Elemental Analysis (%) calc. for C26H23As: C,

76.09; H, 5.65; As, 18.26. Found: C, 75.75; H, 5.72. 76.09; H, 5.65; As, 18.26. Found: C, 75.75; H,

5.72.

2-Diphenylarsino-2’,4’,6’-trimethylbiphenyl (L4). Compound L4 was obtained


mixture by silica-gel column chromatography (petroleum ether), yielding 0.3607 g of

the product (85 % yield). After crystallization from CH3CN needle-shaped crystals

AsPh2

AsPh2

AsPh2


4

were obtained (mp 118.9-119.5 °C). 1H-NMR (CDCl3): δ 7.39-7.36 (1 H, m); 7.29-7.22 (13 H, m); 7.09

(1H, d, 3J = 7.6); 6.87 (2 H, s); 2.33 (3 H, s); 1.77 (6 H, s). 13C-NMR (CDCl3): δ 146.72; 140.05;

139.87; 138.55; 137.00; 136.17; 134.29; 133.77; 129.52; 129.03; 128.48; 128.18; 127.91; 127.25;

21.22; 20.70. NMR 2D (COSY-45) δH /δH: 1.77 / 2.33; 1.77 / 6.87; 2.33 / 6.87; 7.09 / 7.39; 7.26 / 7.09;

7.27 / 7.38. NMR 2D (HSQC) δH /δC: 1.77 / 20.70; 2.33 / 21.22; 6.87 / 127.91; 7.09 / 129.52; 7.26 /

127.25; 7.38 / 129.03. NMR 2D (HMBC) δH /δC: 1.77 / 127.91; 1.77 / 136.17; 1.77 / 138.55; 2.33 /

127.91; 2.33 / 137.00; 6.87 / 127.91; 6.87 / 138.55; 7.09 / 127.25; 7.09 / 140.05; 7.38 / 134.29. MS: m/z (%): 425 (29), 424 (84), 410 (18), 409 (75), 270 (19), 269 (37), 255 (100), 227 (13), 194 (22), 193

(27), 179 (44), 178 (31), 165 (22), 152 (20), 91 (9). HRMS (EI): calcd. for C27H26As 425.1245, found

[M-H]+ 425.1235. Elemental Analysis (%) calc. for C27H25As: C, 76.41; H, 5.94; As, 17.65. Found: C,

76.15; H, 6.02.

2-Diphenylarsino-2’-methoxybiphenyl (L5). Compound L5 was obtained


mixture by silica-gel column chromatography (petroleum ether), yielding 0.3629 g

(88 % yield) of the product as an amorphous white solid (mp 87.6-89 ºC). 1H-NMR

(CDCl3): δ 7.38 (1 H, td; 3J = 7.5 Hz; 4J = 1.4 Hz); 7.32-7.16 (14 H, m); 7.09 (1 H,

dd, 3J = 7.5 Hz; 4J = 1.6 Hz); 6.91 (1 H, td, 3J = 7.4 Hz; 4J = 1.0 Hz); 6.82 (1 H, d, 3J = 8 Hz); 3.40 (3 H,

s). 13C-NMR (CDCl3): δ 156.58; 144.66; 140.96; 140.29; 140.10; 134.20; 133.74; 131.45; 130.99;

130.21; 129.09; 128.53; 128.44; 128.35; 128.06; 127.94; 127.49; 120.10; 110.26; 54.80. NMR 2D

(COSY-45) δH /δH: 3.40 / 6.83; 6.82 / 7.30; 6.91 / 7.08; 6.91 / 7.30; 7.10 / 7.30. NMR 2D (HSQC) δH /δC:

3.40 / 54.8; 6.82 / 110.27; 6.91 / 120.10; 7.08 / 131.45. NMR 2D (HMBC) δH /δC: 3.40 / 156.58; 6.82 /

120.1; 7.09 / 156.59. MS: m/z (%): 412 (9), 382 (30), 381 (100), 303 (6), 257 (24), 243 (11), 228 (10),

227 (23), 213 (13), 168 (11), 152 (16), 151 (9), 139 (9), 78 (4), 51 (5). HRMS (EI): calcd. for

C25H22AsO 413.0881, found [M-H]+ 413.0888. Elemental Analysis (%) calc. for C25H21AsO: C, 72.82;

H, 5.13; As, 18.17; O, 3.88. Found: C, 72.95; H, 5.35.

2-Diphenylarsino-2’,6’-dimethoxybiphenyl (L6). Compound L6 was obtained


mixture by silica-gel column chromatography (petroleum ether), yielding 0.4203 g

of the product (95 % yield). After crystallization from CH3CN cubic crystals were

obtained (mp 133.0-133.8 °C). 1H-NMR (CDCl3): δ 7.41-7.39 (1 H, m); 7.29-7.22

(13 H, m); 7.18-7.16 (1 H, m); 6.53 (2 H, d, 3J = 8.8 Hz); 3.46 (6 H, s). 13C-NMR (CDCl3): δ 157.83;

140.80; 140.63; 133.97; 133.74; 130.81; 129.20; 128.45; 128.24; 127.83; 127.37; 119.30; 103.57;

55.39. NMR 2D (COSY-45) δH /δH: 3.46 / 6.52; 3.46 / 7.26; 6.52 / 7.28; 7.17 / 7.25; 7.17 / 7.40; 7.25 /

7.40. NMR 2D (HSQC) δH /δC: 3.46 / 55.39; 6.56 / 103.57; 7.17 / 133.97; 7.40 / 129.20. MS: m/z (%):

442 (8), 411 (100), 396 (8), 273 (8), 257 (8), 227 (12), 214 (10), 152 (7), 77 (5), 51 (6). HRMS (EI): calcd. for C26H24AsO2 443.0987, found [M-H]+ 443.0998. Elemental Analysis (%) calc. for

C26H23AsO2: C, 70.59; H, 5.24; As, 16.94; O, 7.23. Found: C, 70.65; H, 5.13.

AsPh2

MeO

AsPh2

MeO OMe


5

1-(2-Diphenylarsinophenyl)naphthalene (L7). Compound L7 was obtained


mixture by silica-gel column chromatography (petroleum ether), obtaining 0.3026 g

of the product (70 % yield). After extensive drying with vacuum pump, L7 was

obtained as an amorphous white solid (mp 50-53 °C). 1H-NMR (CDCl3): δ 7.87-

7.81 (2 H, m); 7.46-7.10 (20 H, m). 13C-NMR (CDCl3): δ 145.99; 140.67; 140.30; 139.98; 139.57;

133.99; 133.76; 133.72; 133.35; 132.35; 130.62; 128.51; 128.36; 128.26; 128.20; 128.06; 127.89;

127.86; 127.81; 126.38; 125.83; 125.66; 124.68. MS: m/z (%): 433 (15), 432 (51), 354 (10), 279 (14),

278 (45), 277 (100), 202 (75), 177 (14). HRMS (EI): calcd. for C28H22As 433.0932, found [M-H]+

433.0918. Elemental Analysis (%) calc. for C28H21As: C, 77.78; H, 4.90; As, 17.33. Found: C, 77.86;

H, 4.72.

AsPh2


6

3. NMR Spectroscopy

2-Diphenylarsino-2’-methylbiphenyl (L2) 1H NMR (CDCl3).

9.5

9.0

8.5

8.0

7.5

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5

ppm

0.0380.115

1.300

1.571

2.050

6.9046.9237.0407.0587.0767.1817.2007.2197.2397.2637.2817.2947.3067.3177.3337.3437.3847.4027.422

0.200.11

0.76

0.60

3.00

1.001.08

16.72

6.9

7.0

7.1

7.2

7.3

7.4

7.5

7.6

ppm

6.9046.9237.0407.0587.0767.1817.2007.2197.2397.2637.2817.2947.3067.3177.3337.3437.3847.4027.422

AsPh2


7

2-Diphenylarsino-2’-methylbiphenyl (L2) 13C NMR (CDCl3).

2030

4050

6070

8090

100

110

120

130

140

150

160

170

180

190

200

210

ppm

20.51

29.83

125.05127.57127.74128.51129.62129.80130.43133.84133.94134.00136.03139.69139.90139.95141.61147.45

AsPh2

124

126

128

130

132

134

136

138

140

142

144

146

148

150

ppm

125.05

127.57127.74128.51

129.62129.80130.43

133.84133.94134.00

136.03

139.69139.90139.95

141.61

147.45


8

2-Diphenylarsino-2’-methylbiphenyl (L2) NMR 2D (COSY-45) (CDCl3).

pp

m

8.

07

.5

7.

06

.5

6.

05

.5

5.

04

.5

4.

03

.5

3.

02

.5

2.

01

.5

1.

00

.5

0.

0p

pm

8.

0

7.

5

7.

0

6.

5

6.

0

5.

5

5.

0

4.

5

4.

0

3.

5

3.

0

2.

5

2.

0

1.

5

1.

0

0.

5

0.

0

AsPh2


9

2-Diphenylarsino-2’-methylbiphenyl (L2) NMR 2D (COSY-45) (CDCl3).

ppm

6.66.76.86.97.07.17.27.37.47.57.67.77.87.98.0 ppm8.0

7.5

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5

0.0

ppm

6.66.76.86.97.07.17.27.37.47.57.67.77.87.98.0 ppm

6.6

6.7

6.8

6.9

7.0

7.1

7.2

7.3

7.4

7.5

7.6

7.7

7.8

7.9

8.0

AsPh2


10

2-Diphenylarsino-2’-methylbiphenyl (L2) NMR 2D (HSQC) (CDCl3).

ppm

8.0

7.5

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5

0.0

ppm20 40 60 80 100

120

140

160

180

AsPh2

ppm

6.7

6.8

6.9

7.0

7.1

7.2

7.3

7.4

7.5

7.6

7.7

ppm

120

122

124

126

128

130

132

134

136

138

140

142

144


11

2-Diphenylarsino-2’,6’-dimethylbiphenyl (L3) 1H NMR (CDCl3).

8.0

7.5

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5

0.0

ppm

0.000

1.546

1.792

7.0247.0437.0957.1137.1717.1907.2097.2227.2347.2417.2467.2717.2877.2927.3717.3827.390

6.00

17.31

7.0

7.1

7.2

7.3

7.4

7.5

ppm

7.0247.043

7.0957.113

7.1717.1907.2097.2227.2347.2417.2467.2717.2877.2927.3717.3827.3907.3997.403

AsPh2


12

2-Diphenylarsino-2’,6’-dimethylbiphenyl (L3) 13C NMR (CDCl3).

180

170

160

150

140

130

120

110

100

9080

7060

5040

3020

10pp

m

20.77

76.7277.0477.35

127.10127.34127.51128.22128.50129.05129.22133.80134.27136.39139.72139.89141.35146.60

130

135

140

145

ppm

127.10127.34127.51128.22128.50129.05129.22

133.80134.27

136.39

139.72139.89141.35

146.60

AsPh2


13

2-Diphenylarsino-2’,6’-dimethylbiphenyl (L3) NMR 2D (COSY-45) (CDCl3).

pp

m

1.

52

.0

2.

53

.0

3.

54

.0

4.

55

.0

5.

56

.0

6.

57

.0

7.

5p

pm

1.

5

2.

0

2.

5

3.

0

3.

5

4.

0

4.

5

5.

0

5.

5

6.

0

6.

5

7.

0

7.

5

AsPh2


14

2-Diphenylarsino-2’,6’-dimethylbiphenyl (L3) NMR 2D (HSQC) (CDCl3).

ppm

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

6.5

7.0

7.5

ppm20 40 60 80 100

120

140

AsPh2

ppm

6.95

7.00

7.05

7.10

7.15

7.20

7.25

7.30

7.35

7.40

7.45

7.50

7.55

ppm

120

125

130

135

140

145

150


15

2-Diphenylarsino-2’,6’-dimethylbiphenyl (L3) NMR 2D (HMBC) (CDCl3).

ppm

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

6.5

7.0

7.5

ppm20 30 40 50 60 70 80 90 100

110

120

130

140

150

AsPh2


16

2-Diphenylarsino-2’,4’,6’-trimethylbiphenyl (L4) 1H NMR (CDCl3).

8.0

7.5

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5

0.0

ppm

-0.001

1.5631.766

2.334

6.8687.0837.1017.2237.2347.2427.2477.2547.2657.2747.2787.2867.2927.3597.3687.3737.378

6.00

2.96

1.951.12

13.74

6.9

7.0

7.1

7.2

7.3

7.4

ppm

6.868

7.0837.1017.2237.2347.2427.2477.2547.2657.2747.2787.2867.2927.3597.3687.3737.378

AsPh2


17

2-Diphenylarsino-2’,4’,6’-trimethylbiphenyl (L4) 13C NMR (CDCl3).

180

170

160

150

140

130

120

110

100

9080

7060

5040

3020

10pp

m

20.7021.22

76.7277.03

127.25127.91128.18128.48129.03129.52133.77134.29136.17137.00138.55139.87140.05146.72

130

132

134

136

138

140

142

144

146

ppm127.25

127.91128.18128.48129.03129.52

133.77134.29

136.17137.00

138.55139.87140.05

146.72

1820

2224

26pp

m

20.7021.22

AsPh2


18

2-Diphenylarsino-2’,4’,6’-trimethylbiphenyl (L4) NMR 2D (COSY-45) (CDCl3).

pp

m

8.

58

.0

7.

57

.0

6.

56

.0

5.

55

.0

4.

54

.0

3.

53

.0

2.

52

.0

1.

51

.0

0.

50

.0

pp

m

8.

5

8.

0

7.

5

7.

0

6.

5

6.

0

5.

5

5.

0

4.

5

4.

0

3.

5

3.

0

2.

5

2.

0

1.

5

1.

0

0.

5

0.

0

AsPh2

pp

m

6.

56

.6

6.

76

.8

6.

97

.0

7.

17

.2

7.

37

.4

7.

57

.6

7.

77

.8

7.

9p

pm

6.

6

6.

7

6.

8

6.

9

7.

0

7.

1

7.

2

7.

3

7.

4

7.

5

7.

6

7.

7

7.

8

7.

9

8.

0


19

2-Diphenylarsino-2’,4’,6’-trimethylbiphenyl (L4) NMR 2D (HSQC) (CDCl3).

AsPh2

ppm

1.0

1.2

1.4

1.6

1.8

2.0

2.2

2.4

2.6

2.8

3.0

3.2

ppm

18.5

19.0

19.5

20.0

20.5

21.0

21.5

22.0

22.5

23.0

23.5

24.0

ppm

6.7

6.8

6.9

7.0

7.1

7.2

7.3

7.4

7.5

7.6

ppm

124

126

128

130

132

134

136

138

140

142

144

ppm

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

6.5

7.0

7.5

8.0

8.5

ppm20 30 40 50 60 70 80 90 100

110

120

130

140

150


20

2-Diphenylarsino-2’,4’,6’-trimethylbiphenyl (L4) NMR 2D (HMBC) (CDCl3).

ppm

6.26.36.46.56.66.76.86.97.07.17.27.37.47.57.67.77.87.98.08.1 ppm

125

130

135

140

145

150

AsPh2


21

2-Diphenylarsino-2’,4’,6’-trimethylbiphenyl (L4) NMR 2D (HMBC) (CDCl3).

AsPh2

ppm

-1.0-0.55.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

125

130

135

140

145

150


22

2-Diphenylarsino-2’-methoxybiphenyl (L5) 1H NMR (CDCl3).

8.0

7.5

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5

ppm

0.000

3.403

6.8116.8126.8326.8336.8906.8936.9096.9126.9286.9307.0817.0867.1007.1047.1617.1647.1807.1837.2027.2107.2187.2217.2367.2407.255

3.00

0.981.001.05

14.97

6.8

6.9

7.0

7.1

7.2

7.3

7.4

ppm6.812

6.8326.8336.9096.9127.0817.0867.1807.1837.2107.2187.2217.2367.2407.2557.2587.2827.2867.2977.3007.3057.307

AsPh2

MeO


23

2-Diphenylarsino-2’-methoxybiphenyl (L5) 13C NMR (CDCl3).

180

170

160

150

140

130

120

110

100

9080

7060

5040

3020

10pp

m

54.80

77.07

110.26120.10127.49127.94128.06128.35128.44128.53129.09130.21130.99131.45133.74134.20140.10140.29140.96144.66156.58

128

129

130

131

132

133

134

135

136

137

138

139

140

141

ppm

127.49127.94128.06128.35128.44128.53129.09

130.21

130.99

131.45

133.74

134.20

140.10140.29

140.96

AsPh2

MeO


24

2-Diphenylarsino-2’-methoxybiphenyl (L5) NMR 2D (COSY-45) (CDCl3).

pp

m

1.

01

.5

2.

02

.5

3.

03

.5

4.

04

.5

5.

05

.5

6.

06

.5

7.

07

.5

8.

0p

pm

1.

0

1.

5

2.

0

2.

5

3.

0

3.

5

4.

0

4.

5

5.

0

5.

5

6.

0

6.

5

7.

0

7.

5

8.

0

pp

m

6.

66

.7

6.

86

.9

7.

07

.1

7.

27

.3

7.

47

.5

7.

67

.7

7.

8p

pm

6.

6

6.

7

6.

8

6.

9

7.

0

7.

1

7.

2

7.

3

7.

4

7.

5

7.

6

7.

7

7.

8

AsPh2

MeO


25

2-Diphenylarsino-2’-methoxybiphenyl (L5) NMR 2D (HSQC) (CDCl3).

ppm

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

6.5

7.0

7.5

8.0

ppm20 40 60 80 100

120

140

160

180

200

ppm

6.6

6.7

6.8

6.9

7.0

7.1

7.2

7.3

7.4

7.5

7.6

7.7

ppm

105

110

115

120

125

130

135

140

145

AsPh2

MeO


26

2-Diphenylarsino-2’-methoxybiphenyl (L5) NMR 2D (HMBC) (CDCl3).

ppm

6.6

6.7

6.8

6.9

7.0

7.1

7.2

7.3

7.4

7.5

7.6

7.7

ppm

105

110

115

120

125

130

135

140

145

150

155

160

165

AsPh2

MeO

ppm

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

6.5

7.0

7.5

8.0

ppm20 40 60 80 100

120

140

160

180

200


27

2-Diphenylarsino-2’,6’-dimethoxybiphenyl (L6) 1H NMR (CDCl3).

AsPh2

MeO OMe

8.0

7.5

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5

ppm

-0.002

1.523

3.456

6.5166.5377.1577.1607.1767.1817.2217.2257.2297.2417.2477.2487.2527.2697.2767.2977.3907.393

6.00

1.95

15.24

6.6

6.8

7.0

7.2

7.4

ppm6.516

6.5377.1577.1607.1767.1817.2217.2257.2297.2417.2477.2487.2527.2697.2767.2977.3907.3937.3957.410


28

2-Diphenylarsino-2’,6’-dimethoxybiphenyl (L6) 13C NMR (CDCl3).

2030

4050

6070

8090

100

110

120

130

140

150

160

170

180

190

200

210

ppm

55.39

76.7177.0377.35

103.57

119.30127.37127.83128.24128.45129.20130.81133.74133.97140.63140.80

157.83

128

129

130

131

132

133

134

135

136

137

138

139

140

ppm

127.37127.83128.24128.45

129.20

130.81

133.74133.97

140.63140.80

AsPh2

MeO OMe


29

2-Diphenylarsino-2’,6’-dimethoxybiphenyl (L6) NMR 2D (COSY-45) (CDCl3).

pp

m

3.

54

.0

4.

55

.0

5.

56

.0

6.

57

.0

7.

5p

pm

3.

5

4.

0

4.

5

5.

0

5.

5

6.

0

6.

5

7.

0

7.

5

AsPh2

MeO OMep

pm

6.

26

.4

6.

66

.8

7.

07

.2

7.

47

.6

7.

8p

pm

6.

2

6.

4

6.

6

6.

8

7.

0

7.

2

7.

4

7.

6

7.

8


30

2-Diphenylarsino-2’,6’-dimethoxybiphenyl (L6) NMR 2D (HSQC) (CDCl3).

ppm

4.5

5.0

5.5

6.0

6.5

7.0

7.5

8.0

8.5

9.0

ppm60 70 80 90 100

110

120

130

140

150

160

AsPh2

MeO OMe


31

1-(2-Diphenylarsinophenyl)naphthalene (L7) 1H NMR (CDCl3).

AsPh2

1110

98

76

54

32

1pp

m0.000

1.540

7.1047.1207.1347.1387.1837.1997.2217.2287.2347.2417.2457.2557.2637.2667.2877.2957.3087.3127.3207.3287.3347.3387.3497.3547.3667.4157.4357.4447.4527.4657.8147.8357.8457.865

20.62

2.00

7.1

7.2

7.3

7.4

7.5

7.6

7.7

7.8

7.9

ppm7.120

7.1347.1387.1837.1997.2417.2457.2557.2637.2667.2877.2957.3087.3127.3287.3347.3497.3547.4157.4357.444


32

1-(2-Diphenylarsinophenyl)naphthalene (L7) 13C NMR (CDCl3).

2030

4050

6070

8090

100

110

120

130

140

150

ppm

76.7077.0277.33

124.68125.66125.83126.38127.81127.86127.89128.06128.20128.26128.36128.51130.62132.35133.35133.72133.76133.99139.57139.98140.30

AsPh2


33

1-(2-Diphenylarsinophenyl)naphthalene (L7) 13C NMR (CDCl3).

125

126

127

128

129

130

131

132

133

134

135

136

137

138

139

140

141

ppm

124.68

125.66125.83

126.38

127.81127.86127.89128.06128.20128.26128.36128.51

130.62

132.35

133.35133.72133.76133.99

139.57139.98140.30140.67

AsPh2


34

1-(2-Diphenylarsinophenyl)naphthalene (L7) NMR 2D (HSQC) (CDCl3).

ppm

8.5

8.0

7.5

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5

0.0

ppm

220

200

180

160

140

120

10080604020

ppm

6.7

6.8

6.9

7.0

7.1

7.2

7.3

7.4

7.5

7.6

7.7

7.8

7.9

8.0

8.1

ppm

115

120

125

130

135

140

145

150

AsPh2


35

4. References

1 Uberman, P. M.; Lanteri, M. N.; Martin, S. E. Organometallics 2009, 28, 6927-6934. 2 Lanteri, M. N.; Rossi, R. A.; Martín, S. E. J. Organomet. Chem., 2009, 694, 3425-3430.


synthesis of biphenyl-based arsine ligands by suzuki

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