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

Cite this

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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",

author = "Jonathan Clayden and William Farnaby and Grainger, \{Damian M.\} and Ulrich Hennecke and Michele Mancinelli and Tetlow, \{Daniel J.\} and Hillier, \{Ian H.\} and Vincent, \{Mark A.\}",

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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doi = "10.1021/ja808959e",

language = "English",

volume = "131",

pages = "3410--3411",

journal = "Journal of the American Chemical Society",

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TY - JOUR

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

UR - https://www.scopus.com/pages/publications/70149123601

U2 - 10.1021/ja808959e

DO - 10.1021/ja808959e

M3 - Article

AN - SCOPUS:70149123601

SN - 0002-7863

VL - 131

SP - 3410

EP - 3411

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: α-arylation of benzylic alcohols

Abstract

Keywords

ASJC Scopus subject areas

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