Regio- and Enantioselective Epoxy Ring Opening of
2,3-Epoxy-3-phenyl Alcohols/Carboxylic Acids and Their Derivatives

Zhan, Xiaoyan

doi:10.1134/s107042802004017x

Cited by 4 publications

(1 citation statement)

References 63 publications

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“…1b ). As an alternative, by harnessing ring-strain release 28 – 31 , small heterocycles such as epoxide and aziridine could also readily participate in nucleophilic displacement of those strained C–N/O bond 32 , 33 . However, the ring-opening cleavage of C–C bond embedded in small carbocycles such as cyclopropane is relatively underexplored except for those electronically biased donor-acceptor ones 34 – 37 .…”

Section: Introductionmentioning

confidence: 99%

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

Zhang

Pan

et al. 2022

Nat Commun

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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 SN2-type ring-opening functionalization manifold, while the regioselectivity is subjected to an orbital control scenario.

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