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Site‐ and Stereoselective C(<i>sp</i><sup>3</sup>)−H Borylation of Strained (Hetero)Cycloalkanols Enabled by Iridium Catalysis

Qian Gao, Senmiao Xu

2022Angewandte Chemie International Edition45 citationsDOI

Abstract

Abstract Transition metal‐catalyzed site‐ and stereoselective C−H activation of strained (hetero)cycloalkanes remains a formidable challenge. We herein report a carbamate‐directed iridium‐catalyzed asymmetric β−C( sp 3 )−H borylation of cyclopropanol derivatives. A variety of densely functionalized cyclopropanols were obtained in good enantioselectivities via desymmetrization and kinetic resolution. In addition, site‐selective C( sp 3 )−H borylation of methine groups furnished α‐borylated (hetero)cycloalkanols in moderate to good yields. The synthetic utility of the method was further shown in a gram‐scale synthesis and diverse downstream transformations of borylated products.

Topics & Concepts

BorylationDesymmetrizationChemistryIridiumStereoselectivityCatalysisKinetic resolutionCombinatorial chemistryOrganic chemistryMedicinal chemistryEnantioselective synthesisStereochemistryArylAlkylCatalytic C–H Functionalization MethodsCatalytic Cross-Coupling ReactionsOrganoboron and organosilicon chemistry
Site‐ and Stereoselective C(<i>sp</i><sup>3</sup>)−H Borylation of Strained (Hetero)Cycloalkanols Enabled by Iridium Catalysis | Litcius