Photoredox-catalyzed C-C bond cleavage of cyclopropanes for the formation of C(sp³)-heteroatom bonds.

ABSTRACT: Sterically congested C-O and C-N bonds are ubiquitous in natural products, pharmaceuticals, and bioactive compounds. However, the development of a general method for the efficient construction of those sterically demanding covalent bonds still remains a formidable challenge. Herein, a photoredox-driven ring-opening C(sp³)-heteroatom bond formation of arylcyclopropanes is presented, which enables the construction of structurally diversified while sterically congested dialkyl ether, alkyl ester, alcohol, amine, chloride/fluoride, azide and also thiocyanate derivatives. The selective single electron oxidation of aryl motif associated with the thermodynamic driving force from ring strain-release is the key for this transformation. By this synergistic activation mode, C-C bond cleavage of otherwise inert cyclopropane framework is successfully unlocked. Further mechanistic and computational studies disclose a complete stereoinversion upon nucleophilic attack, thus proving a concerted S_N2-type ring-opening functionalization manifold, while the regioselectivity is subjected to an orbital control scenario.

SUBMITTER: Ge L 

PROVIDER: S-EPMC9547854 | biostudies-literature | 2022 Oct

REPOSITORIES: biostudies-literature