Thieme Journal Awardees - Where Are They Now? On Cobalt-Catalyzed Biaryl Coupling Reactions

Abstract

An operationally simple biaryl coupling reaction has been developed. The underlying domino process involves in situ Grignard formation from aryl bromides and subsequent homocoupling with catalytic CoCl₂ and 1 bar synthetic air as terminal oxidant.

Key words

domino reactions - cross-coupling - Grignard reactions - biaryls - dimerizations

References and Notes

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10

The current world market prices of palladium (370 USD/oz) and nickel (14.4 USD/lb) are expected to increase due to the request from emerging countries such as China, Russia, India, and Brazil.

19

General Procedure
A 10 mL flask was charged with Mg ribbons (74 mg, 3.0 mmol), fitted with a rubber septum, and purged with argon (1 min). Dry THF (4 mL) and the arylbromide (2.5 mmol) were added via a syringe. The solution was stirred at r.t. for 1-3 h under argon. Cooled to 0 ˚C, a solution of CoCl₂ (16.1 mg, 0.12 mmol, 5 mol%) in dry THF (6 mL) was added. Synthetic air (20 mL/min) was added through a needle to the solution. After 0.5-3 h, the reaction was quenched with sat. aq NH₄Cl (5 mL), extracted with EtOAc (3 × 10 mL).
The combined organic phases were dried (Na₂SO₄), concentrated, and subjected to flash chromatography (cyclohexene-EtOAc).
New Compounds
3′,3′′-Difluoro[1,1′:4,1′′:4′,1′′′]quarter-phenyl (2n): mp 182 ˚C. ^¹H NMR (300 MHz, CDCl₃): δ = 7.75 (d, 4 H, J = 6 Hz), 7.65-7.05 (m, 12 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 160.0 (d, J = 246 Hz), 140.4 (d, J = 6.8 Hz), 135.3 (d, J = 12.4 Hz), 131.1 (d, J = 3.4 Hz), 128.9, 128.5, 128.1, 122.7, 114.4 (d, J = 24.1 Hz). MS (EI, 70 eV): m/z (%) = 342 (100) [M⁺], 320 (7), 264 (5), 170 (7), 77 (5). HRMS: m/z = 342.122. IR (ATR): 1550 (m), 1473 (s), 1403 (m), 1246 (m), 1183 (m), 1130 (m), 1040 (m), 911 (s), 823 (s), 766 (s), 695 (s) cm^-¹.
3,3′,4,4′-Tetrafluorobiphenyl (2g): mp 83 ˚C; ^¹H NMR (300 MHz, CDCl₃): δ = 7.39-7.32 (m, 2 H), 7.30-7.25 (m, 4 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 152.1 (dd, J = 12.7, 23.9 Hz), 148.8 (dd, J = 12.6, 24.8 Hz), 136.2, 123.0 (q, J = 3.4 Hz), 117.8 (d, J = 17.3 Hz), 116.0 (d, J = 17.9 Hz). MS (EI, 70 eV): m/z (%) = 226 (100 [M⁺], 206 (22), 175 (8), 156 (7), 138 (7), 112 (8). HRMS: m/z = 226.041. IR (ATR): 3064 (w), 1881 (w), 1599 (s), 1495 (s), 1339 (s), 1316 (m), 1265 (s), 1184 (s), 1150 (m), 117 (s), 1028 (m), 943 (m), 909 (m), 885 (m), 865 (s), 805 (s), 766 (s), 739 (s) cm^-¹.