期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 136, 期 47, 页码 16588-16593出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja508718m
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资金
- National Institute of General Medical Sciences of the National Institutes of Health [R01-GM62871, F32-GM105295]
- Gordon and Betty Moore Foundation
- Beckman Institute
- Sanofi Aventis Bioengineering Research Program at Caltech
- Department of Energy's Office of Biological and Environmental Research
- National Institutes of Health
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-Br bond occurs through a bimetallic mechanism. In particular, we have crystallographically characterized a diamagnetic arylnickel(II) complex, [(i-Pr-pybox)(NiPh)-Ph-II]BArF4, and furnished support for [(i-Pr-pybox)(NiPh)-Ph-II](+) 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)(NiPh)-Ph-I), which has previously been suggested to be an intermediate in nickel-catalyzed cross-couplings, oxidatively adding alkyl electrophiles through a monometallic pathway.
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