Controlling chemoselectivity in the lithiation of substituted aromatic tertiary amides

被引：22

作者：

Armstrong, DR

Boss, SR

Clayden, J

Haigh, R

Kirmani, BA

Linton, DJ

Schooler, P

Wheatley, AEH

机构：

[1] Univ Cambridge, Dept Chem, Cambridge CB2 1EW, England

[2] Univ Strathclyde, Dept Pure & Appl Chem, Glasgow G1 1XL, Lanark, Scotland

[3] Univ Manchester, Dept Chem, Manchester M13 9PL, Lancs, England

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2004年 / 43卷 / 16期

关键词：

density functional calculations; directing groups; lithiation; reaction mechanisms; solid-state structures;

D O I：

10.1002/anie.200353324

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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.

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收藏

页码：2135 / 2138

页数：4

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