Ni-Catalyzed Reductive Dicarbofunctionalization of Nonactivated Alkenes: Scope and Mechanistic Insights
Top Cited Papers
- 21 August 2019
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 141 (35), 13812-13821
- https://doi.org/10.1021/jacs.9b02973
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 thermodynamically 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.Keywords
Funding Information
- Schweizerischer Nationalfonds zur F?rderung der Wissenschaftlichen Forschung (200020_146853)
- Ministerio de Ciencia e Innovaci?n (CTQ2016-79826-R)
- H2020 European Research Council (307948)
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