Nickel-Catalyzed Negishi Arylations of Propargylic Bromides: A聽Mechanistic Investigation
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- 作者：Nathan D. Schley ; Gregory C. Fu
- 刊名：Journal of the American Chemical Society
- 出版年：2014
- 出版时间：November 26, 2014
- 年：2014
- 卷：136
- 期：47
- 页码：16588-16593
- 全文大小：528K
- ISSN：1520-5126
文摘
Although nickel-catalyzed stereoconvergent couplings of racemic alkyl electrophiles are emerging as a powerful tool in organic chemistry, to date there have been no systematic mechanistic studies of such processes. Herein, we examine the pathway for enantioselective Negishi arylations of secondary propargylic bromides, and we provide evidence for an unanticipated radical chain pathway wherein oxidative addition of the C鈥揃r bond occurs through a bimetallic mechanism. In particular, we have crystallographically characterized a diamagnetic arylnickel(II) complex, [(i-Pr-pybox)NiIIPh]BArF4, and furnished support for [(i-Pr-pybox)NiIIPh]+ being the predominant nickel-containing species formed under the catalyzed conditions as well as a key player in the cross-coupling mechanism. On the other hand, our observations do not require a role for an organonickel(I) intermediate (e.g., (i-Pr-pybox)NiIPh), which has previously been suggested to be an intermediate in nickel-catalyzed cross-couplings, oxidatively adding alkyl electrophiles through a monometallic pathway.