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

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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… Click to show full 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.

Keywords: functionalization unactivated; unactivated sp3; site selective; sp3 bonds; selective functionalization; site

Journal Title: Journal of the American Chemical Society
Year Published: 2022

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