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Iron-Catalyzed Photoinduced LMCT: A 1° C–H Abstraction Enables Skeletal Rearrangements and C(sp 3 )–H Alkylation

2021; American Chemical Society; Volume: 11; Issue: 12 Linguagem: Inglês

10.1021/acscatal.1c02285

2155-5435

Yi Cheng Kang, Sean M. Treacy, Tomislav Rovis,

Synthesis and Catalytic Reactions

Herein we disclose an iron-catalyzed method to access skeletal rearrangement reactions akin to the Dowd-Beckwith ring expansion from unactivated C(sp3)-H bonds. Photoinduced ligand-to-metal charge transfer at the iron center generates a chlorine radical, which abstracts electron-rich C(sp3)-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 protodemetallation allows 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.