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^*, William Farnaby, Damian M. Grainger, Ulrich Hennecke, Michele Mancinelli, Daniel J. Tetlow, Ian H. Hillier, Mark A. Vincent

^*Corresponding author for this work

School of Chemistry

Research output: Contribution to journal › Article (Academic Journal) › 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

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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.",

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.}",

year = "2009",

month = mar,

day = "18",

doi = "10.1021/ja808959e",

language = "English",

volume = "131",

pages = "3410--3411",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "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.

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.

UR - http://www.scopus.com/inward/record.url?scp=70149123601&partnerID=8YFLogxK

U2 - 10.1021/ja808959e

DO - 10.1021/ja808959e

M3 - Article (Academic Journal)

C2 - 19275248

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

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