Synlett 2018; 29(09): 1199-1202
DOI: 10.1055/s-0037-1609337
letter
© Georg Thieme Verlag Stuttgart · New York

A Highly Active Cobalt Catalyst System for Kumada Biaryl Cross-Coupling

Wenqin Wu
Institute of Chemical and Engineering Sciences (ICES), Agency for Science, Technology and Research (A*STAR), 8 Biomedical Grove, Neuros, #07-01, Singapore 138665, Republic of Singapore   Email: [email protected]
,
Institute of Chemical and Engineering Sciences (ICES), Agency for Science, Technology and Research (A*STAR), 8 Biomedical Grove, Neuros, #07-01, Singapore 138665, Republic of Singapore   Email: [email protected]
› Author Affiliations
The financial support for this work was provided by “GSK-EDB Singapore Partnership for Green and Sustainable Manufacturing” and the Institute of Chemical and Engineering Sciences (ICES), Agency for Science, Technology and Research (A*STAR), Singapore.
Further Information

Publication History

Received: 25 January 2018

Accepted after revision: 10 February 2018

Publication Date:
06 March 2018 (online)


Abstract

A highly active cobalt catalyst system has been developed for the cross-coupling reactions of arylmagnesium reagents and aryl bromides. In the presence of 1 mol% CoCl2, 2 mol% IPr·HCl and 2 mol% NaO t Bu, a wide range of (hetero)biaryls are prepared in 51–99% yields at room temperature within a short reaction time.

Supporting Information

 
  • References and Notes


    • For recent reviews on iron-catalyzed cross-coupling reactions, see:
    • 2a Adams CJ. Bedford RB. Carter E. Gower NJ. Haddow MF. Harvey JN. Huwe M. Cartes MA. Mansell SM. Mendoza C. Murphy DM. Neeve EC. Nunn J. J. Am. Chem. Soc. 2012; 134: 10333
    • 2b Nakamura E. Hatakeyama T. Ito S. Ishizuka K. Ilies L. Nakamura M. Iron-Catalyzed Cross-Coupling Reactions, in Organic Reactions 2014; 83: 1
    • 2c Kuzmina OM. Steib AK. Moyeux A. Cahiez G. Knochel P. Synthesis 2015; 47: 1696
    • 2d Bauer I. Knölker H.-M. Chem. Rev. 2015; 115: 3170
    • 2e Guérinot A. Cossy J. Top. Curr. Chem. 2016; 374: 49

      For reviews on cobalt-catalyzed cross-coupling reactions, see:
    • 3a Gosmini C. Bégouin J.-M. Moncomble A. Chem. Commun. 2008; 44: 3221
    • 3b Cahiez G. Moyeux A. Chem. Rev. 2010; 110: 1435
    • 4a Magano J. Dunetz JR. Chem. Rev. 2011; 111: 2177
    • 4b Slagt VF. de Vries AH. M. de Vries JG. Kellogg RM. Org. Process Res. Dev. 2010; 14: 30
    • 4c Ivica C. Synthesis of Biaryls . Elsevier; Oxford: 2004

      For examples on iron-catalyzed homocoupling of arylmagnesium reagents, see:
    • 5a Nagano T. Hayashi T. Org. Lett. 2005; 7: 491
    • 5b Cahiez G. Chaboche C. Mahuteau-Betzer F. Ahr M. Org. Lett. 2005; 7: 1943
    • 5c Cahiez G. Moyeux A. Buendia J. Duplais C. J. Am. Chem. Soc. 2007; 129: 13788

    • For an example on cobalt-catalyzed homocoupling of arylmagnesium reagents, see:
    • 5d Kharasch MS. Fuchs CF. J. Am. Chem. Soc. 1941; 63: 2316
    • 6a Hatakeyama T. Nakamura M. J. Am. Chem. Soc. 2007; 129: 9844
    • 6b Hatakeyama T. Hashimoto S. Ishizuka K. Nakamura M. J. Am. Chem. Soc. 2009; 131: 11949

    • Also, see:
    • 6c Agrawal T. Cook SP. Org. Lett. 2014; 16: 5080
    • 7a Chua Y.-Y. Duong HA. Chem. Commun. 2014; 50: 8424
    • 7b Chua Y.-Y. Duong HA. Chem. Commun. 2016; 52: 1466
    • 7c Wu W. Teng Q. Chua Y.-Y. Huynh HV. Duong HA. Organometallics 2017; 36: 2293
  • 8 General Experimental Procedure In a 25 mL Schlenk flask, a mixture of CoCl2 (2 mg, 0.015 mmol, 1 mol%), NaO t Bu (3 mg, 0.03 mmol, 2 mol%) and IPr·HCl (13 mg, 0.03 mmol, 2 mol%) in THF (1.0 mL) was stirred under argon at rt for 1 h. A solution of bromobenzene (1a, 236 mg, 1.5 mmol, 1.0 equiv) in 0.5 mL THF was added followed by a solution of p-tolylmagnesium bromide (2a, 2.3 mL, 0.78 M in THF, 1.8 mmol, 1.2 equiv). The reaction progress was monitored by GC using dodecane as an internal standard. Once completed, the reaction mixture was quenched with saturated aqueous NH4Cl solution (10 mL) and extracted with ethyl acetate (20 mL) three times. The combined organic layers were dried over anhydrous magnesium sulfate and concentrated in vacuo. The resulting crude mixture was purified by silica gel column chromatography to give 3a (237 mg, 94%) as a white solid. Analytical Data for Compound 3a 1H NMR (400 MHz, CDCl3): δ = 7.68–7.59 (m, 2 H), 7.58–7.51 (m, 2 H), 7.47 (dd, J = 8.5, 6.9 Hz, 2 H), 7.38 (d, J = 7.3 Hz, 1 H), 7.30 (d, J = 7.9 Hz, 2 H), 2.45 (s, 3 H). 13C{1 H} NMR (101 MHz, CDCl3): δ = 141.3, 138.5, 137.1, 129.6, 128.8, 127.2, 127.1, 127.0, 126.9, 21.2.
    • 9a Xie L.-G. Wang Z.-X. Chem. Eur. J. 2010; 16: 10332
    • 9b Liu N. Wang Z.-X. J. Org. Chem. 2011; 76: 10031