Highly Active Nickel Catalysts for C鈥揌 Functionalization Identified through Analysis of Off-Cycle Intermediates

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• 作者：Alex J. Nett ; Wanxiang Zhao ; Paul M. Zimmerman ; John Montgomery
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：June 24, 2015
• 年：2015
• 卷：137
• 期：24
• 页码：7636-7639
• 全文大小：311K
• ISSN：1520-5126

文摘

An inhibitory role of 1,5-cyclooctadiene (COD) in nickel-catalyzed C鈥揌 functionalization processes was identified and studied. The bound COD participates in C鈥揌 activation by capturing the hydride, leading to a stable off-cycle 蟺-allyl complex that greatly diminished overall catalytic efficiency. Computational studies elucidated the origin of the effect and enabled identification of a 1,5-hexadiene-derived pre-catalyst that avoids the off-cycle intermediate and provides catalytic efficiencies that are superior to those of catalysts derived from Ni(COD)₂.