N to C Aryl Migration in Lithiated Carbamates: alpha-Arylation of Benzylic Alcohols
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...
Published in: | Journal of the American Chemical Society |
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Main Authors: | , , , , , , , |
Format: | Article in Journal/Newspaper |
Language: | English |
Published: |
2009
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Subjects: | |
Online Access: | https://research.manchester.ac.uk/en/publications/4867edee-793a-4090-acb0-15083fa1be2c https://doi.org/Doi 10.1021/Ja808959e |
Summary: | 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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