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

JLG Ruano; D Barros; MC Maestro; Alexandra Martha Zoya Slawin; PCB Page

doi:10.1021/jo000494i

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

JLG Ruano, D Barros, MC Maestro, Alexandra Martha Zoya Slawin, PCB Page

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

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	The Journal of Organic Chemistry
Volume	65
DOIs	https://doi.org/10.1021/jo000494i
Publication status	Published - 22 Sept 2000

Keywords

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

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@article{62c9580ea41547ceb402735a1aad4abe,

title = "High stereocontrol in aldol reactions with ketones: enantioselective synthesis of beta-hydroxy gamma-ketoesters by ester enolate 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, CHIRAL LEWIS-ACIDS, C-2-SYMMETRICAL COPPER(II) COMPLEXES, 1,3-DITHIANE 1-OXIDE, PYRUVATE ESTERS, 2-ACYL-1,3-DITHIANE 1-OXIDES, GRIGNARD-REAGENTS, DERIVATIVES, ADDITIONS, ENOLSILANES",

author = "JLG Ruano and D Barros and MC Maestro and Slawin, \{Alexandra Martha Zoya\} and PCB Page",

year = "2000",

month = sep,

day = "22",

doi = "10.1021/jo000494i",

language = "English",

volume = "65",

pages = "6027--6034",

journal = "The Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "American Chemical Society (ACS)",

}

TY - JOUR

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

AU - Ruano, JLG

AU - Barros, D

AU - Maestro, MC

AU - Slawin, Alexandra Martha Zoya

AU - Page, PCB

PY - 2000/9/22

Y1 - 2000/9/22

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.

KW - ASYMMETRIC BUILDING-BLOCK

KW - CHIRAL LEWIS-ACIDS

KW - C-2-SYMMETRICAL COPPER(II) COMPLEXES

KW - 1,3-DITHIANE 1-OXIDE

KW - PYRUVATE ESTERS

KW - 2-ACYL-1,3-DITHIANE 1-OXIDES

KW - GRIGNARD-REAGENTS

KW - DERIVATIVES

KW - ADDITIONS

KW - ENOLSILANES

UR - https://www.scopus.com/pages/publications/0034703425

U2 - 10.1021/jo000494i

DO - 10.1021/jo000494i

M3 - Article

SN - 0022-3263

VL - 65

SP - 6027

EP - 6034

JO - The Journal of Organic Chemistry

JF - The Journal of Organic Chemistry

ER -

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

Abstract

Keywords

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