N to C aryl migration in lithiated carbamates: α-arylation of benzylic alcohols

Jonathan Clayden; William Farnaby; Damian M. Grainger; Ulrich Hennecke; Michele Mancinelli; Daniel J. Tetlow; Ian H. Hillier; Mark A. Vincent

doi:10.1021/ja808959e

N to C aryl migration in lithiated carbamates: α-arylation of benzylic alcohols

Jonathan Clayden (Lead / Corresponding author), William Farnaby, Damian M. Grainger, Ulrich Hennecke, Michele Mancinelli, Daniel J. Tetlow, Ian H. Hillier, Mark A. Vincent

Biological Chemistry and Drug Discovery

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

46 Citations (Scopus)

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 @,@-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)	3410-3411
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	131
Issue number	10
Early online date	18 Feb 2009
DOIs	https://doi.org/10.1021/ja808959e
Publication status	Published - 18 Mar 2009

Keywords

Solvents
Additives
Alcohols
Organic compounds
Rearrangement

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja808959e

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title = "N to C aryl migration in lithiated carbamates: α-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 @,@-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 = "Solvents, Additives, Alcohols, Organic compounds, Rearrangement",

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note = "{\textcopyright} 2009 American Chemical Society We are grateful to the Deutscher Akademischer Austauschdienst (DAAD) for a postdoctoral fellowship (to U.H.) and to the EPSRC and the Leverhulme Trust for support.",

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T1 - N to C aryl migration in lithiated carbamates

T2 - α-arylation of benzylic alcohols

AU - Clayden, Jonathan

AU - Farnaby, William

AU - Grainger, Damian M.

AU - Hennecke, Ulrich

AU - Mancinelli, Michele

AU - Tetlow, Daniel J.

AU - Hillier, Ian H.

AU - Vincent, Mark A.

N1 - © 2009 American Chemical Society We are grateful to the Deutscher Akademischer Austauschdienst (DAAD) for a postdoctoral fellowship (to U.H.) and to the EPSRC and the Leverhulme Trust for support.

PY - 2009/3/18

Y1 - 2009/3/18

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 @,@-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 @,@-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 - Solvents

KW - Additives

KW - Alcohols

KW - Organic compounds

KW - Rearrangement

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JF - Journal of the American Chemical Society

IS - 10

ER -

N to C aryl migration in lithiated carbamates: α-arylation of benzylic alcohols

Abstract

Keywords

ASJC Scopus subject areas

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