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Nickel-Catalyzed Negishi Arylations of Propargylic Bromides: A Mechanistic Investigation

Schley, Nathan D. and Fu, Gregory C. (2014) Nickel-Catalyzed Negishi Arylations of Propargylic Bromides: A Mechanistic Investigation. Journal of the American Chemical Society, 136 (47). pp. 16588-16593. ISSN 0002-7863. PMCID PMC4277758. doi:10.1021/ja508718m.

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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)NiIIPh]BAr^F_4, 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.

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Fu, Gregory C.0000-0002-0927-680X
Additional Information:© 2014 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: August 24, 2014; Published: November 17, 2014. This work was supported by the National Institute of General Medical Sciences of the National Institutes of Health (R01-GM62871 to G.C.F. and Ruth L. Kirschstein National Research Service Award F32-GM105295 to N.D.S.). We thank Trixia M. Buscagan (preliminary results), Dr. Ivory Hills (preliminary results), Dr. Angel J. Di Bilio (EPR), Lawrence M. Henling (X-ray crystallography), Prof. Jonas C. Peters (discussions and equipment), Dr. Christopher Uyeda (electrochemistry), and Dr. David VanderVelde (NMR). We acknowledge the Gordon and Betty Moore Foundation, the Beckman Institute, and the Sanofi–Aventis Bioengineering Research Program at Caltech for their support of the Molecular Observatory at Caltech. The SSRL is supported by the Department of Energy’s Office of Biological and Environmental Research as well as by the National Institutes of Health.
Funding AgencyGrant Number
NIH Predoctoral FellowshipF32-GM105295
Gordon and Betty Moore FoundationUNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
Sanofi-Aventis Bioengineering Research ProgramUNSPECIFIED
Department of Energy (DOE)UNSPECIFIED
Issue or Number:47
PubMed Central ID:PMC4277758
Record Number:CaltechAUTHORS:20141125-080958357
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Official Citation:Nickel-Catalyzed Negishi Arylations of Propargylic Bromides: A Mechanistic Investigation Nathan D. Schley and Gregory C. Fu Journal of the American Chemical Society 2014 136 (47), 16588-16593
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:52121
Deposited By: Ruth Sustaita
Deposited On:25 Nov 2014 20:42
Last Modified:10 Nov 2021 19:21

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