Work

Generation of α‐Boryl Radicals by H. Transfer and their Use in Cycloisomerizations

Year: 2021

Type: article

Abstract: Carbon‐centered radicals can be stabilized by delocalization of their spin density into the vacant p orbital of a boron substituent. α‐Vinyl boronates, in particular pinacol (Bpin) derivatives, are excellent hydrogen atom acceptors. Under H2, in the presence of a cobaloxime catalyst, they generate α‐boryl radicals; these species can undergo 5‐exo radical cyclizations if appropriate double bond acceptors are present, leading to densely functionalized heterocycles with tertiary substituents on Bpin. The reaction shows good functional group tolerance with wide scope, and the resulting boronate products can be converted into other useful functionalities.

Source: Angewandte Chemie International Edition

DOI: 10.1002/anie.202107665

Authors: Shicheng Shi, Farbod Salahi, Hunter B. Vibbert, Maleeha Rahman, Scott A. Snyder, Jack R. Norton

Institutions: Columbia University, University of Chicago, Barnard College

Language: English

Topic: Radical Photochemical Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: National Institutes of Health, National Institute of General Medical Sciences

Award: Catalysis of Tin-Free Radical Reactions Under H2