Nickel-Catalyzed Cross-Couplings of Organosilicon Reagents with Unactivated Secondary Alkyl Bromides
David A. Powell and Gregory C. Fu*
*Department of Chemistry, Massachusetts Institute of Technology, Cambridge,
Massachusetts 02139, Email: gcf
mit.edu
D. A. Powell, G. C. Fu, J. Am. Chem. Soc., 2004, 126, 7788-7789.
DOI: 10.1021/ja047433c
Abstract
A nickel-catalyzed cross-coupling of organosilicon compounds with alkyl halides offers a broad substrate scope (secondary electrophiles and functional-group compatibility) and a remarkable air stability of the catalyst components.
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Details
This document discusses the development of a nickel-catalyzed method for cross-coupling unactivated secondary alkyl halides with organosilicon reagents, a significant advancement in synthetic chemistry. The research, conducted by David A. Powell and Gregory C. Fu at MIT, addresses the challenges of coupling secondary alkyl halides, which have been difficult due to issues like slow oxidative addition and rapid elimination. Previous successful couplings were limited to organozinc, organoboron, and Grignard reagents. The new method employs a nickel-based catalyst, specifically NiBr2-diglyme with bathophenanthroline, achieving high yields and functional-group tolerance. The study highlights the importance of reaction parameters, showing that the absence of key components like NiBr2-diglyme or bathophenanthroline results in significantly lower yields. The method is versatile, applicable to various secondary alkyl bromides and iodides, and primary alkyl halides, demonstrating compatibility with functional groups such as ethers, imides, ketones, and carbamates. This development expands the scope of metal-catalyzed cross-coupling reactions, offering a practical and efficient approach for synthetic chemists. The research was supported by the NIH, the Natural Sciences and Engineering Research Council of Canada, Merck, and Novartis.
Room-Temperature Hiyama Cross-Couplings of Arylsilanes with Alkyl Bromides and Iodides
J.-Y. Lee, G. C. Fu, J. Am. Chem. Soc., 2003, 125, 5616-5617.
F. González-Bobes, G. C. Fu, J. Am. Chem. Soc., 2006, 128, 5360-5361.
Key Words
Hiyama Coupling, Silanes, Arenes
ID: J48-Y2004-1530
