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Ni-Catalyzed Reductive Dicarbofunctionalization of Nonactivated Alkenes: Scope and Mechanistic Insights


Shu, Wei; García-Domínguez, Andrés; Quirós, M Teresa; Mondal, Rahul; Cárdenas, Diego J; Nevado, Cristina (2019). Ni-Catalyzed Reductive Dicarbofunctionalization of Nonactivated Alkenes: Scope and Mechanistic Insights. Journal of the American Chemical Society, 141(35):13812-13821.

Abstract

Olefins devoid of directing or activating groups have been dicarbofunctionalized here with two electrophilic carbon sources under reductive conditions. Simultaneous formation of one C(sp3)-C(sp3) and one C(sp3)-C(sp2) bond across a variety of unbiased π-systems proceeds with exquisite selectivity by the combination of a Ni catalyst with TDAE as sacrificial reductant. Control experiments and computational studies revealed the feasibility of a radical-based mechanism involving, formally, two interconnected Ni(I)/Ni(III) processes and demonstrated the different ability of Ni(I) species (Ni(I)I vs. PhNi(I)) to reduce the C(sp3)-I bond. The role of the reductant was also investigated in depth, suggesting that a one-electron reduction of Ni(II) species to Ni(I) is thermody-namically favored. Further, the preferential activation of alkyl vs. aryl halides by ArNi(I) complexes as well as the high affinity of ArNi(II) for secondary over tertiary C-centered radicals explains the lack of undesired homo- and direct coupling products (Ar-Ar, Ar-Alk) in these transformations.

Abstract

Olefins devoid of directing or activating groups have been dicarbofunctionalized here with two electrophilic carbon sources under reductive conditions. Simultaneous formation of one C(sp3)-C(sp3) and one C(sp3)-C(sp2) bond across a variety of unbiased π-systems proceeds with exquisite selectivity by the combination of a Ni catalyst with TDAE as sacrificial reductant. Control experiments and computational studies revealed the feasibility of a radical-based mechanism involving, formally, two interconnected Ni(I)/Ni(III) processes and demonstrated the different ability of Ni(I) species (Ni(I)I vs. PhNi(I)) to reduce the C(sp3)-I bond. The role of the reductant was also investigated in depth, suggesting that a one-electron reduction of Ni(II) species to Ni(I) is thermody-namically favored. Further, the preferential activation of alkyl vs. aryl halides by ArNi(I) complexes as well as the high affinity of ArNi(II) for secondary over tertiary C-centered radicals explains the lack of undesired homo- and direct coupling products (Ar-Ar, Ar-Alk) in these transformations.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > Catalysis
Physical Sciences > General Chemistry
Life Sciences > Biochemistry
Physical Sciences > Colloid and Surface Chemistry
Uncontrolled Keywords:Colloid and Surface Chemistry, Biochemistry, General Chemistry, Catalysis
Language:English
Date:4 September 2019
Deposited On:29 Jul 2020 09:20
Last Modified:30 Jul 2020 20:00
Publisher:American Chemical Society (ACS)
ISSN:0002-7863
Additional Information:This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/jacs.9b02973
OA Status:Green
Publisher DOI:https://doi.org/10.1021/jacs.9b02973
Project Information:
  • : FunderSNSF
  • : Grant ID200020_146853
  • : Project TitleNovel Synthetic Methods based on Gold Catalyzed Reactions
  • : FunderFP7
  • : Grant ID307948
  • : Project TitleNIGOCAT - Nature-Inspired Gold Catalytic Tools

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