The dienolate aldol reaction of (E)-N-crotonoyl C(4)-isopropyl SuperQuat: asymmetric synthesis of alpha-vinyl-beta-hydroxycarboxylic acid derivatives and conversion to alpha-ethylidene-beta-hydroxyesters (beta-substituted Baylis-Hillman products)

Stephen G. Davies; Dirk L. Elend; Simon Jones; Paul M. Roberts; Edward D. Savory; Andrew D. Smith; James E. Thomson

doi:10.1016/j.tet.2009.07.004

The dienolate aldol reaction of (E)-N-crotonoyl C(4)-isopropyl SuperQuat: asymmetric synthesis of alpha-vinyl-beta-hydroxycarboxylic acid derivatives and conversion to alpha-ethylidene-beta-hydroxyesters (beta-substituted Baylis-Hillman products)

Stephen G. Davies, Dirk L. Elend, Simon Jones, Paul M. Roberts, Edward D. Savory, Andrew D. Smith, James E. Thomson

Research output: Contribution to journal › Article › peer-review

18 Citations (Scopus)

Abstract

The synthesis of alpha-vinyl-beta-hydroxyesters and alpha-ethlylidene-beta-hydroxyesters (beta-substituted Baylis-Hillman products) Via the dienolate aldol reaction of (E)-N-crotonoyl C(4)-isopropyl SuperQuat is described. High levels of syn-diastereoselectivity (up to >98% de) are observed for the dienolate aldol reaction with boron enolates, generated either directly with Bu2BOTf or by transmetalation of the potassium enolate with B-bromocatecholborane. Cleavage of the resultant syn-aldol products from the auxiliary gives alpha-vinyl-beta-hydroxyesters in >98% de and >98% ee. Subsequent isomerisation of the double bond into conjugation provides alpha-ethylidene-beta-hydroxyesters (beta-substituted Baylis-Hillman products) in high diastereo- and enantiopurity (>= 91:9 |(E):(Z)| and >98% ee). (C) 2009 Elsevier Ltd. All rights reserved.

Original language	English
Pages (from-to)	7837-7851
Number of pages	15
Journal	Tetrahedron
Volume	65
Issue number	37
DOIs	https://doi.org/10.1016/j.tet.2009.07.004
Publication status	Published - 12 Sept 2009

Keywords

Asymmetric synthesis
SuperQuat
Dienolate aldol
Baylis-Hillman
CORRESPONDING BETA,GAMMA-UNSATURATED ESTERS
CARBON BOND-FORMATION
CONJUGATE ADDITION
(E)-ALPHA,BETA-UNSATURATED ESTERS
STEREOSELECTIVE SYNTHESIS
UNSATURATED ESTERS
CHIRAL AUXILIARY
AMINO ALDEHYDES
LITHIUM
CONDENSATION

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Davies, S. G., Elend, D. L., Jones, S., Roberts, P. M., Savory, E. D., Smith, A. D., & Thomson, J. E. (2009). The dienolate aldol reaction of (E)-N-crotonoyl C(4)-isopropyl SuperQuat: asymmetric synthesis of alpha-vinyl-beta-hydroxycarboxylic acid derivatives and conversion to alpha-ethylidene-beta-hydroxyesters (beta-substituted Baylis-Hillman products). Tetrahedron, 65(37), 7837-7851. https://doi.org/10.1016/j.tet.2009.07.004

@article{7f4be2983a844d2e8c48bf0ae8830d7a,

title = "The dienolate aldol reaction of (E)-N-crotonoyl C(4)-isopropyl SuperQuat: asymmetric synthesis of alpha-vinyl-beta-hydroxycarboxylic acid derivatives and conversion to alpha-ethylidene-beta-hydroxyesters (beta-substituted Baylis-Hillman products)",

abstract = "The synthesis of alpha-vinyl-beta-hydroxyesters and alpha-ethlylidene-beta-hydroxyesters (beta-substituted Baylis-Hillman products) Via the dienolate aldol reaction of (E)-N-crotonoyl C(4)-isopropyl SuperQuat is described. High levels of syn-diastereoselectivity (up to >98% de) are observed for the dienolate aldol reaction with boron enolates, generated either directly with Bu2BOTf or by transmetalation of the potassium enolate with B-bromocatecholborane. Cleavage of the resultant syn-aldol products from the auxiliary gives alpha-vinyl-beta-hydroxyesters in >98% de and >98% ee. Subsequent isomerisation of the double bond into conjugation provides alpha-ethylidene-beta-hydroxyesters (beta-substituted Baylis-Hillman products) in high diastereo- and enantiopurity (>= 91:9 |(E):(Z)| and >98% ee). (C) 2009 Elsevier Ltd. All rights reserved.",

keywords = "Asymmetric synthesis, SuperQuat, Dienolate aldol, Baylis-Hillman, CORRESPONDING BETA,GAMMA-UNSATURATED ESTERS, CARBON BOND-FORMATION, CONJUGATE ADDITION, (E)-ALPHA,BETA-UNSATURATED ESTERS, STEREOSELECTIVE SYNTHESIS, UNSATURATED ESTERS, CHIRAL AUXILIARY, AMINO ALDEHYDES, LITHIUM, CONDENSATION",

author = "Davies, {Stephen G.} and Elend, {Dirk L.} and Simon Jones and Roberts, {Paul M.} and Savory, {Edward D.} and Smith, {Andrew D.} and Thomson, {James E.}",

year = "2009",

month = sep,

day = "12",

doi = "10.1016/j.tet.2009.07.004",

language = "English",

volume = "65",

pages = "7837--7851",

journal = "Tetrahedron",

issn = "0040-4020",

publisher = "Elsevier",

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Davies, SG, Elend, DL, Jones, S, Roberts, PM, Savory, ED, Smith, AD & Thomson, JE 2009, 'The dienolate aldol reaction of (E)-N-crotonoyl C(4)-isopropyl SuperQuat: asymmetric synthesis of alpha-vinyl-beta-hydroxycarboxylic acid derivatives and conversion to alpha-ethylidene-beta-hydroxyesters (beta-substituted Baylis-Hillman products)', Tetrahedron, vol. 65, no. 37, pp. 7837-7851. https://doi.org/10.1016/j.tet.2009.07.004

The dienolate aldol reaction of (E)-N-crotonoyl C(4)-isopropyl SuperQuat: asymmetric synthesis of alpha-vinyl-beta-hydroxycarboxylic acid derivatives and conversion to alpha-ethylidene-beta-hydroxyesters (beta-substituted Baylis-Hillman products). / Davies, Stephen G.; Elend, Dirk L.; Jones, Simon et al.
In: Tetrahedron, Vol. 65, No. 37, 12.09.2009, p. 7837-7851.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - The dienolate aldol reaction of (E)-N-crotonoyl C(4)-isopropyl SuperQuat: asymmetric synthesis of alpha-vinyl-beta-hydroxycarboxylic acid derivatives and conversion to alpha-ethylidene-beta-hydroxyesters (beta-substituted Baylis-Hillman products)

AU - Davies, Stephen G.

AU - Elend, Dirk L.

AU - Jones, Simon

AU - Roberts, Paul M.

AU - Savory, Edward D.

AU - Smith, Andrew D.

AU - Thomson, James E.

PY - 2009/9/12

Y1 - 2009/9/12

N2 - The synthesis of alpha-vinyl-beta-hydroxyesters and alpha-ethlylidene-beta-hydroxyesters (beta-substituted Baylis-Hillman products) Via the dienolate aldol reaction of (E)-N-crotonoyl C(4)-isopropyl SuperQuat is described. High levels of syn-diastereoselectivity (up to >98% de) are observed for the dienolate aldol reaction with boron enolates, generated either directly with Bu2BOTf or by transmetalation of the potassium enolate with B-bromocatecholborane. Cleavage of the resultant syn-aldol products from the auxiliary gives alpha-vinyl-beta-hydroxyesters in >98% de and >98% ee. Subsequent isomerisation of the double bond into conjugation provides alpha-ethylidene-beta-hydroxyesters (beta-substituted Baylis-Hillman products) in high diastereo- and enantiopurity (>= 91:9 |(E):(Z)| and >98% ee). (C) 2009 Elsevier Ltd. All rights reserved.

AB - The synthesis of alpha-vinyl-beta-hydroxyesters and alpha-ethlylidene-beta-hydroxyesters (beta-substituted Baylis-Hillman products) Via the dienolate aldol reaction of (E)-N-crotonoyl C(4)-isopropyl SuperQuat is described. High levels of syn-diastereoselectivity (up to >98% de) are observed for the dienolate aldol reaction with boron enolates, generated either directly with Bu2BOTf or by transmetalation of the potassium enolate with B-bromocatecholborane. Cleavage of the resultant syn-aldol products from the auxiliary gives alpha-vinyl-beta-hydroxyesters in >98% de and >98% ee. Subsequent isomerisation of the double bond into conjugation provides alpha-ethylidene-beta-hydroxyesters (beta-substituted Baylis-Hillman products) in high diastereo- and enantiopurity (>= 91:9 |(E):(Z)| and >98% ee). (C) 2009 Elsevier Ltd. All rights reserved.

KW - Asymmetric synthesis

KW - SuperQuat

KW - Dienolate aldol

KW - Baylis-Hillman

KW - CORRESPONDING BETA,GAMMA-UNSATURATED ESTERS

KW - CARBON BOND-FORMATION

KW - CONJUGATE ADDITION

KW - (E)-ALPHA,BETA-UNSATURATED ESTERS

KW - STEREOSELECTIVE SYNTHESIS

KW - UNSATURATED ESTERS

KW - CHIRAL AUXILIARY

KW - AMINO ALDEHYDES

KW - LITHIUM

KW - CONDENSATION

U2 - 10.1016/j.tet.2009.07.004

DO - 10.1016/j.tet.2009.07.004

M3 - Article

SN - 0040-4020

VL - 65

SP - 7837

EP - 7851

JO - Tetrahedron

JF - Tetrahedron

IS - 37

ER -

Davies SG, Elend DL, Jones S, Roberts PM, Savory ED, Smith AD et al. The dienolate aldol reaction of (E)-N-crotonoyl C(4)-isopropyl SuperQuat: asymmetric synthesis of alpha-vinyl-beta-hydroxycarboxylic acid derivatives and conversion to alpha-ethylidene-beta-hydroxyesters (beta-substituted Baylis-Hillman products). Tetrahedron. 2009 Sept 12;65(37):7837-7851. doi: 10.1016/j.tet.2009.07.004