Fast racemisation and slow epimerisation of laterally lithiated amides: Stereochemical evidence for the mechanism of inversion of amide-substituted benzyllithiums

Jonathan Clayden; Christopher C. Stimson; Martine Keenan; Andrew E H Wheatley

doi:10.1039/B310963A

Fast racemisation and slow epimerisation of laterally lithiated amides: Stereochemical evidence for the mechanism of inversion of amide-substituted benzyllithiums

Jonathan Clayden^*
, Christopher C. Stimson
, Martine Keenan
, Andrew E H Wheatley

^*Corresponding author for this work

School of Chemistry

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

23 Citations (Scopus)

Abstract

Tertiary 1-naphthamides racemise much more slowly than their laterally lithiated derivatives, and the relative rates of racemisation and epimerisation of these derivatives indicate that the lithium-bearing stereogenic centre inverts via a "conducted tour" mechanism, in which the lithium cation is delivered from one face to the other by coordination to the rotating amide group.

Original language	English
Pages (from-to)	228-229
Number of pages	2
Journal	Chemical Communications
Volume	10
Issue number	2
Early online date	5 Dec 2003
DOIs	https://doi.org/10.1039/B310963A
Publication status	Published - 21 Jan 2004

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Organic & Biological

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title = "Fast racemisation and slow epimerisation of laterally lithiated amides: Stereochemical evidence for the mechanism of inversion of amide-substituted benzyllithiums",

abstract = "Tertiary 1-naphthamides racemise much more slowly than their laterally lithiated derivatives, and the relative rates of racemisation and epimerisation of these derivatives indicate that the lithium-bearing stereogenic centre inverts via a {"}conducted tour{"} mechanism, in which the lithium cation is delivered from one face to the other by coordination to the rotating amide group.",

author = "Jonathan Clayden and Stimson, \{Christopher C.\} and Martine Keenan and Wheatley, \{Andrew E H\}",

year = "2004",

month = jan,

day = "21",

doi = "10.1039/B310963A",

language = "English",

volume = "10",

pages = "228--229",

journal = "Chemical Communications",

issn = "1359-7345",

publisher = "Royal Society of Chemistry",

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}

Fast racemisation and slow epimerisation of laterally lithiated amides: Stereochemical evidence for the mechanism of inversion of amide-substituted benzyllithiums. / Clayden, Jonathan; Stimson, Christopher C.; Keenan, Martine et al.
In: Chemical Communications, Vol. 10, No. 2, 21.01.2004, p. 228-229.

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

TY - JOUR

T1 - Fast racemisation and slow epimerisation of laterally lithiated amides

T2 - Stereochemical evidence for the mechanism of inversion of amide-substituted benzyllithiums

AU - Clayden, Jonathan

AU - Stimson, Christopher C.

AU - Keenan, Martine

AU - Wheatley, Andrew E H

PY - 2004/1/21

Y1 - 2004/1/21

N2 - Tertiary 1-naphthamides racemise much more slowly than their laterally lithiated derivatives, and the relative rates of racemisation and epimerisation of these derivatives indicate that the lithium-bearing stereogenic centre inverts via a "conducted tour" mechanism, in which the lithium cation is delivered from one face to the other by coordination to the rotating amide group.

AB - Tertiary 1-naphthamides racemise much more slowly than their laterally lithiated derivatives, and the relative rates of racemisation and epimerisation of these derivatives indicate that the lithium-bearing stereogenic centre inverts via a "conducted tour" mechanism, in which the lithium cation is delivered from one face to the other by coordination to the rotating amide group.

UR - https://www.scopus.com/pages/publications/1642439222

U2 - 10.1039/B310963A

DO - 10.1039/B310963A

M3 - Article (Academic Journal)

AN - SCOPUS:1642439222

SN - 1359-7345

VL - 10

SP - 228

EP - 229

JO - Chemical Communications

JF - Chemical Communications

IS - 2

ER -

Fast racemisation and slow epimerisation of laterally lithiated amides: Stereochemical evidence for the mechanism of inversion of amide-substituted benzyllithiums

Abstract

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