Nickel-Catalyzed Cross-Coupling of Diarylborinic Acids with Aryl Chlorides

Abstract

A highly efficient nickel/triarylphosphine catalyst system, Ni[P(4-MeOPh) 3 ] 2 Cl 2 /2P(4-MeOPh) 3 , has been developed for crosscoupling of diarylborinic acids with a wide range of aryl chlorides. A variety of unsymmetrical biaryl and heterobiaryl compounds with various functional groups and steric hindrance could be obtained in good to excellent yields using 0.5−2 mol % catalyst loadings in the presence of K 3 PO 4 •3H 2 O in toluene. The high atom economy of diarylborinic acids and cost-effectiveness of the nickel/ phosphine catalyst system make the cross-coupling truly practical in the production of biaryl fine chemicals. Usefulness of the nickel/phosphine catalyzed cross-coupling of diarylborinic acids with aryl chlorides has been demonstrated in the development of a scalable and economical process for synthesis of 4′-methyl-2-cyanobiphenyl, Sartan biphenyl.

Transition-Metal-Free Cross-Coupling of Aryl Halides with Arylstannanes

“…Treatment of tetra- ( p -methylphenyl)tin 7 (96.6 mg, 0.20 mmol) with 1-methyl-3-iodobenzene 5a (102.7 μL, 174.4 mg, 0.8 mmol) by the Typical Procedure gave 10a (36.4 mg, 25%): 1 H NMR δ 2.41 (s, 3H), 2.43 (s, 3H), 7.16 (d, J = 7.5 Hz, 1H), 7.26 (d, J = 7.8 Hz, 1H), 7.33 (t, J = 7.5 Hz, 1H), 7.40 (d, J = 12.7 Hz, 2H), 7.56 (t, J = 6.5 Hz, 3H); 13 C NMR δ 20.1, 20.5, 123.1, 125.8, 126.0, 126.7, 126.8, 127.6, 128.4, 135.9, 137.2, 140.1. GC-MS ( t R 8.4 min) m / z 182 (100, M + ).…”

Fe(II)/Au(I) Relay Catalyzed Propargylisoxazole to Pyridine Isomerization: Access to 6-Halonicotinates

“…13 C NMR (CDCl 3 , 100 MHz): δ 21.3 (CH 3 ), 52.3 (CH 3 ), 121.2 (CH), 126.8 (C), 128.4 (CH), 128.9 (CH), 137.1 (C), 137.7 (CH), 138.6 (C), 151.2 (CH), 158.7 (C), 168.7 (C). Spectral data were in agreement with previously reported values …”

Nickel‐Catalyzed Decarbonylative Cou­pling of Aryl Esters and Arylboronic Acids

“…3‐(4‐Methyl)pyridine (2c) [4423‐09‐0]: 27 Purification by column chromatography (hexane/EtOAc, 3:1) afforded 2c as a colourless oil (33 mg, 39 %). 1 H NMR (CDCl 3 , 400 MHz, 298 K): δ = 8.84 (s, 1 H), 8.57 (s, 1 H), 7.87–7.85 (d, J = 8.4 Hz, 1 H), 7.49–7.47 (d, J = 7.6 Hz, 2 H), 7.35 (s, 1 H), 7.30–7.26 (d, J = 7.6 Hz, 2 H), 2.41 (s, 3 H) ppm.…”