Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 141, Issue 35, Pages 13812-13821Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.9b02973
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Funding
- European Research Council (ERC) [307948]
- Swiss National Science Foundation [SNF 200020_146853]
- Spanish Ministerio de Economia y Competitividad [CTQ2016-79826-R]
- Juan de la Cierva fellowship
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Olefins devoid of directing or activating groups have been dicarbofunctionalized here with two electrophilic carbon sources under reductive conditions. Simultaneous formation of one C(sp(3))-C(sp(3)) and one C(sp(3))-C(sp(2)) bond across a variety of unbiased pi-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(sp(3))-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.
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