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DOI: 10.1055/s-0029-1218013
Thieme Journal Awardees - Where Are They Now? On Cobalt-Catalyzed Biaryl Coupling Reactions
Publikationsverlauf
Publikationsdatum:
08. Oktober 2009 (online)
![](https://www.thieme-connect.de/media/synlett/200918/lookinside/thumbnails/10.1055-s-0029-1218013-1.jpg)
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
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References and Notes
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.