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Conformational Flexibility as a Tool for Enabling Site-Selective Functionalization of Unactivated sp³ C-O Bonds in Cyclic Acetals.

ABSTRACT: A dual catalytic manifold that enables site-selective functionalization of unactivated sp³ C-O bonds in cyclic acetals with aryl and alkyl halides is reported. The reaction is triggered by an appropriate σ*-p orbital overlap prior to sp³ C-O cleavage, thus highlighting the importance of conformational flexibility in both reactivity and site selectivity. The protocol is characterized by its excellent chemoselectivity profile, thus offering new vistas for activating strong σ sp³ C-O linkages.

SUBMITTER: Romano C

PROVIDER: S-EPMC9264358 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature

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Conformational Flexibility as a Tool for Enabling Site-Selective Functionalization of Unactivated sp3 C-O Bonds in Cyclic Acetals.

Romano Ciro C Talavera Laura L Gómez-Bengoa Enrique E Martin Ruben R

Journal of the American Chemical Society 20220624 26

A dual catalytic manifold that enables site-selective functionalization of unactivated sp3 C-O bonds in cyclic acetals with aryl and alkyl halides is reported. The reaction is triggered by an appropriate σ*-p orbital overlap prior to sp3 C-O cleavage, thus highlighting the importance of conformational flexibility in both reactivity and site selectivity. The protocol is characterized by its excellent chemoselectivity profile, thus offering new vis ...[more]

PMID: 35749319

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