High stereocontrol in aldol reaction with ketones: Enantioselective synthesis of beta-hydroxy gamma-ketoesters by ester enolate aldol reactions with 2-acyl-2-alkyl-1,3-dithiane 1-oxides

José L. G. Ruano; David Barros; M. Carmen Maestro; Alexandra M. Z. Slawin; Philip C. Bulman Page

doi:10.1021/jo000494i

High stereocontrol in aldol reaction with ketones: Enantioselective synthesis of beta-hydroxy gamma-ketoesters by ester enolate aldol reactions with 2-acyl-2-alkyl-1,3-dithiane 1-oxides

José L. G. Ruano, David Barros, M. Carmen Maestro, Alexandra M. Z. Slawin, Philip C. Bulman Page

Chemistry of Materials and Catalysis

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

22 Citations (Scopus)

Abstract

The asymmetric aldol reaction of 1,2-diketones, masked as nonracemic 2-acyl dithiane oxides, with lithium enolates derived from several esters and lactones, proceeds with a high degree of stereocontrol at both carbonyl and enolate prochiral centers, the stereocontrol mainly determined by the configuration of the sulfoxide sulfur atom. The sense of induced stereochemistry observed for ester enolates is different from that seen for lactone enolates. Hydrolysis of the dithiane oxide units of the major diastereoisomerically pure aldol products affords enantiomerically pure tertiary alpha-substituted beta-hydroxy-gamma-ketoesters.

Original language	English
Pages (from-to)	6027-6034
Number of pages	8
Journal	Journal of Organic Chemistry
Volume	65
Issue number	19
DOIs	https://doi.org/10.1021/jo000494i
Publication status	Published - 2000

Keywords

ASYMMETRIC BUILDING-BLOCK
C-2-SYMMETRICAL
3-DITHIANE 1-OXIDES
2-ACYL-1
ENOLSILANES
GRIGNARD-REAGENTS
1
3-DITHIANE 1-OXIDE
CHIRAL LEWIS-ACIDS
DERIVATIVES
PYRUVATE ESTERS
COPPER(II) COMPLEXES
ADDITIONS

Access to Document

10.1021/jo000494i

Cite this

@article{37e9f33b14af436bb5ca811e48940800,

title = "High stereocontrol in aldol reaction with ketones: Enantioselective synthesis of beta-hydroxy gamma-ketoesters by ester enolate aldol reactions with 2-acyl-2-alkyl-1,3-dithiane 1-oxides",

abstract = "The asymmetric aldol reaction of 1,2-diketones, masked as nonracemic 2-acyl dithiane oxides, with lithium enolates derived from several esters and lactones, proceeds with a high degree of stereocontrol at both carbonyl and enolate prochiral centers, the stereocontrol mainly determined by the configuration of the sulfoxide sulfur atom. The sense of induced stereochemistry observed for ester enolates is different from that seen for lactone enolates. Hydrolysis of the dithiane oxide units of the major diastereoisomerically pure aldol products affords enantiomerically pure tertiary alpha-substituted beta-hydroxy-gamma-ketoesters.",

keywords = "ASYMMETRIC BUILDING-BLOCK, C-2-SYMMETRICAL, 3-DITHIANE 1-OXIDES, 2-ACYL-1, ENOLSILANES, GRIGNARD-REAGENTS, 1, 3-DITHIANE 1-OXIDE, CHIRAL LEWIS-ACIDS, DERIVATIVES, PYRUVATE ESTERS, COPPER(II) COMPLEXES, ADDITIONS",

author = "Ruano, {Jos{\'e} L. G.} and David Barros and Maestro, {M. Carmen} and Slawin, {Alexandra M. Z.} and {Bulman Page}, {Philip C.}",

year = "2000",

doi = "10.1021/jo000494i",

language = "English",

volume = "65",

pages = "6027--6034",

journal = "Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "American Chemical Society",

number = "19",

}

High stereocontrol in aldol reaction with ketones: Enantioselective synthesis of beta-hydroxy gamma-ketoesters by ester enolate aldol reactions with 2-acyl-2-alkyl-1,3-dithiane 1-oxides. / Ruano, José L. G.; Barros, David; Maestro, M. Carmen et al.

In: Journal of Organic Chemistry, Vol. 65, No. 19, 2000, p. 6027-6034.

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

TY - JOUR

T1 - High stereocontrol in aldol reaction with ketones: Enantioselective synthesis of beta-hydroxy gamma-ketoesters by ester enolate aldol reactions with 2-acyl-2-alkyl-1,3-dithiane 1-oxides

AU - Ruano, José L. G.

AU - Barros, David

AU - Maestro, M. Carmen

AU - Slawin, Alexandra M. Z.

AU - Bulman Page, Philip C.

PY - 2000

Y1 - 2000

N2 - The asymmetric aldol reaction of 1,2-diketones, masked as nonracemic 2-acyl dithiane oxides, with lithium enolates derived from several esters and lactones, proceeds with a high degree of stereocontrol at both carbonyl and enolate prochiral centers, the stereocontrol mainly determined by the configuration of the sulfoxide sulfur atom. The sense of induced stereochemistry observed for ester enolates is different from that seen for lactone enolates. Hydrolysis of the dithiane oxide units of the major diastereoisomerically pure aldol products affords enantiomerically pure tertiary alpha-substituted beta-hydroxy-gamma-ketoesters.

AB - The asymmetric aldol reaction of 1,2-diketones, masked as nonracemic 2-acyl dithiane oxides, with lithium enolates derived from several esters and lactones, proceeds with a high degree of stereocontrol at both carbonyl and enolate prochiral centers, the stereocontrol mainly determined by the configuration of the sulfoxide sulfur atom. The sense of induced stereochemistry observed for ester enolates is different from that seen for lactone enolates. Hydrolysis of the dithiane oxide units of the major diastereoisomerically pure aldol products affords enantiomerically pure tertiary alpha-substituted beta-hydroxy-gamma-ketoesters.

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KW - C-2-SYMMETRICAL

KW - 3-DITHIANE 1-OXIDES

KW - 2-ACYL-1

KW - ENOLSILANES

KW - GRIGNARD-REAGENTS

KW - 1

KW - 3-DITHIANE 1-OXIDE

KW - CHIRAL LEWIS-ACIDS

KW - DERIVATIVES

KW - PYRUVATE ESTERS

KW - COPPER(II) COMPLEXES

KW - ADDITIONS

U2 - 10.1021/jo000494i

DO - 10.1021/jo000494i

M3 - Article

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SP - 6027

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JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

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