N to C Aryl Migration in Lithiated Carbamates: alpha-Arylation of Benzylic Alcohols

J Clayden; W Farnaby; D M Grainger; U Hennecke; M Mancinelli; D J Tetlow; I H Hillier; M A Vincent

doi:Doi 10.1021/Ja808959e

N to C Aryl Migration in Lithiated Carbamates: alpha-Arylation of Benzylic Alcohols

J Clayden, W Farnaby, D M Grainger, U Hennecke, M Mancinelli, D J Tetlow, I H Hillier, M A Vincent

Research output: Contribution to journal › Article › peer-review

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.

Original language	English
Pages (from-to)	3410-+
Journal	Journal of the American Chemical Society
Volume	131
Issue number	10
DOIs	https://doi.org/Doi 10.1021/Ja808959e
Publication status	Published - 2009

Keywords

metalated nitrogen derivatives
electrophilic substitution
enantioselective synthesis
organozinc addition
tertiary alcohols
organic-synthesis
carbonic-acid
ketones
rearrangement
diarylmethylamines

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Doi 10.1021/Ja808959e

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title = "N to C Aryl Migration in Lithiated Carbamates: alpha-Arylation of Benzylic Alcohols",

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.",

keywords = "metalated nitrogen derivatives, electrophilic substitution, enantioselective synthesis, organozinc addition, tertiary alcohols, organic-synthesis, carbonic-acid, ketones, rearrangement, diarylmethylamines",

author = "J Clayden and W Farnaby and Grainger, {D M} and U Hennecke and M Mancinelli and Tetlow, {D J} and Hillier, {I H} and Vincent, {M A}",

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TY - JOUR

T1 - N to C Aryl Migration in Lithiated Carbamates: alpha-Arylation of Benzylic Alcohols

AU - Clayden, J

AU - Farnaby, W

AU - Grainger, D M

AU - Hennecke, U

AU - Mancinelli, M

AU - Tetlow, D J

AU - Hillier, I H

AU - Vincent, M A

N1 - 427QA Times Cited:5 Cited References Count:31

PY - 2009

Y1 - 2009

N2 - 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.

AB - 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.

KW - metalated nitrogen derivatives

KW - electrophilic substitution

KW - enantioselective synthesis

KW - organozinc addition

KW - tertiary alcohols

KW - organic-synthesis

KW - carbonic-acid

KW - ketones

KW - rearrangement

KW - diarylmethylamines

U2 - Doi 10.1021/Ja808959e

DO - Doi 10.1021/Ja808959e

M3 - Article

SN - 1520-5126

VL - 131

SP - 3410-+

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 10

ER -

N to C Aryl Migration in Lithiated Carbamates: alpha-Arylation of Benzylic Alcohols

Abstract

Keywords

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