Controlling chemoselectivity in the lithiation of substituted aromatic tertiary amides

David R. Armstrong; Sally R. Boss; Jonathan Clayden; Robert Haigh; Basel A. Kirmani; David J. Linton; Paul Schooler; Andrew E H Wheatley

doi:10.1002/anie.200353324

Controlling chemoselectivity in the lithiation of substituted aromatic tertiary amides

David R. Armstrong, Sally R. Boss^*, Jonathan Clayden, Robert Haigh, Basel A. Kirmani, David J. Linton, Paul Schooler, Andrew E H Wheatley

^*Corresponding author for this work

School of Chemistry

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

27 Citations (Scopus)

Abstract

Solvent effects control the regioselectivity with which tert-butyllithium deprotonates 2-ethyl-N,N-diisopropyl-1-benzamide. From THF an ortho-lithiated dimer is isolated but from N,N,N′,N″, N″pentamethyldiethylenetriamine (pmdeta) a laterally lithiated monomer is obtained (see scheme). Density functional theory (DFT) calculations point to the importance of Lewis base solvation and aggregation state in determining the chemoselectivity.

Original language	English
Pages (from-to)	2135-2138
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	43
Issue number	16
Early online date	6 Apr 2004
DOIs	https://doi.org/10.1002/anie.200353324
Publication status	Published - 13 Apr 2004

Keywords

Density functional calculations
Directing groups
Lithiation
Reaction mechanisms
Solid-state structures

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title = "Controlling chemoselectivity in the lithiation of substituted aromatic tertiary amides",

abstract = "Solvent effects control the regioselectivity with which tert-butyllithium deprotonates 2-ethyl-N,N-diisopropyl-1-benzamide. From THF an ortho-lithiated dimer is isolated but from N,N,N′,N″, N″pentamethyldiethylenetriamine (pmdeta) a laterally lithiated monomer is obtained (see scheme). Density functional theory (DFT) calculations point to the importance of Lewis base solvation and aggregation state in determining the chemoselectivity.",

keywords = "Density functional calculations, Directing groups, Lithiation, Reaction mechanisms, Solid-state structures",

author = "Armstrong, {David R.} and Boss, {Sally R.} and Jonathan Clayden and Robert Haigh and Kirmani, {Basel A.} and Linton, {David J.} and Paul Schooler and Wheatley, {Andrew E H}",

year = "2004",

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language = "English",

volume = "43",

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journal = "Angewandte Chemie - International Edition",

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T1 - Controlling chemoselectivity in the lithiation of substituted aromatic tertiary amides

AU - Armstrong, David R.

AU - Boss, Sally R.

AU - Clayden, Jonathan

AU - Haigh, Robert

AU - Kirmani, Basel A.

AU - Linton, David J.

AU - Schooler, Paul

AU - Wheatley, Andrew E H

PY - 2004/4/13

Y1 - 2004/4/13

N2 - Solvent effects control the regioselectivity with which tert-butyllithium deprotonates 2-ethyl-N,N-diisopropyl-1-benzamide. From THF an ortho-lithiated dimer is isolated but from N,N,N′,N″, N″pentamethyldiethylenetriamine (pmdeta) a laterally lithiated monomer is obtained (see scheme). Density functional theory (DFT) calculations point to the importance of Lewis base solvation and aggregation state in determining the chemoselectivity.

AB - Solvent effects control the regioselectivity with which tert-butyllithium deprotonates 2-ethyl-N,N-diisopropyl-1-benzamide. From THF an ortho-lithiated dimer is isolated but from N,N,N′,N″, N″pentamethyldiethylenetriamine (pmdeta) a laterally lithiated monomer is obtained (see scheme). Density functional theory (DFT) calculations point to the importance of Lewis base solvation and aggregation state in determining the chemoselectivity.

KW - Density functional calculations

KW - Directing groups

KW - Lithiation

KW - Reaction mechanisms

KW - Solid-state structures

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U2 - 10.1002/anie.200353324

DO - 10.1002/anie.200353324

M3 - Article (Academic Journal)

AN - SCOPUS:4544361332

SN - 1433-7851

VL - 43

SP - 2135

EP - 2138

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 16

ER -

Controlling chemoselectivity in the lithiation of substituted aromatic tertiary amides

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Keywords

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