Iron-Catalyzed Photoinduced LMCT: A 1° C–H Abstraction Enables Skeletal Rearrangements and C(sp3)–H Alkylation
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- 8 June 2021
- journal article
- research article
- Published by American Chemical Society (ACS) in ACS Catalysis
- Vol. 11 (12), 7442-7449
- https://doi.org/10.1021/acscatal.1c02285
Abstract
Herein we disclose an iron-catalyzed method to access skeletal rearrangement reactions akin to the Dowd-Beckwith ring expansion from unactivated C(sp(3))-H bonds. Photoinduced ligand-to-metal charge transfer at the iron center generates a chlorine radical, which abstracts electron-rich C(sp(3))-H bonds. The resulting unstable alkyl radicals can undergo rearrangement in the presence of suitable functionality. Addition to an electron deficient olefin, recombination with a photoreduced iron complex, and subsequent protodemetalation allow for redox-neutral alkylation of the resulting radical. Simple adjustments to the reaction conditions enable the selective synthesis of the directly alkylated or the rearranged-alkylated products. As a radical clock, these rearrangements also enable the measurement of rate constants of addition into various electron deficient olefins in the Giese reaction.Funding Information
- National Institute of General Medical Sciences (GM125206)
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