N to C aryl migration in lithiated carbamates: alpha-arylation of benzylic alcohols
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Updated: Jun 25, 2026

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
Published on: April 19, 2019
Jonathan Clayden1, William Farnaby, Damian M Grainger
1School of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, UK. clayden@man.ac.uk
Abstract:
We report a new mode of reactivity displayed by lithiated O-benzyl carbamates carrying an N-aryl substituent: upon lithiation, the N-aryl group is transferred cleanly from N to C. An arylation of the carbamate results, providing a route to alpha,alpha-arylated secondary or tertiary alcohols. We also report density functional theory calculations supporting the proposal that arylation proceeds through a dearomatizing attack on the aromatic ring, a significantly lower energy pathway than the 1,2-acyl transfer observed with related N-alkyl carbamates.
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