Catalytic asymmetric epoxidation of α,β-unsaturated esters with chiral yttrium-biaryldiol complexes

Hiroyuki Kakei, Riichiro Tsuji, Takashi Ohshima, Hiroyuki Morimoto, Shigeki Matsunaga, Masakatsu Shibasaki

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

The full details of the asymmetric epoxidation of α,β- unsaturated esters catalyzed by yttrium complexes with biaryldiol ligands are described. An yttrium-biphenyldiol catalyst, generated from Y(OiPr) 3-biphenyldiol ligand-triphenylarsine oxide (1:1:1), is suitable for the epoxidation of various α,β-unsaturated esters. With this catalyst, β-aryl α,β-unsaturated esters gave high enantioselectivities and good yields (≤99% ee). The reactivity of this catalyst is good, and the catalyst loading could be decreased to as little as 0.5-2 mol % (the turnover number was up to 116), while high enantiomeric excesses were maintained. For β-alkyl α,β-unsaturated esters, an yttrium-binol catalyst, generated from Y-(OiPr)3-binol ligand-triphenylphosphine oxide (1:1:2), gave the best enantioselectivities (≤97% ee). The utility of the epoxidation reaction was demonstrated in an efficient synthesis of (-)-ragaglitazar, a potential antidiabetes agent.

Original languageEnglish
Pages (from-to)257-264
Number of pages8
JournalChemistry - An Asian Journal
Volume2
Issue number2
DOIs
Publication statusPublished - Jul 2 2007
Externally publishedYes

Fingerprint

Yttrium
Epoxidation
Esters
Catalysts
Ligands
Enantioselectivity
Oxides

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Organic Chemistry

Cite this

Catalytic asymmetric epoxidation of α,β-unsaturated esters with chiral yttrium-biaryldiol complexes. / Kakei, Hiroyuki; Tsuji, Riichiro; Ohshima, Takashi; Morimoto, Hiroyuki; Matsunaga, Shigeki; Shibasaki, Masakatsu.

In: Chemistry - An Asian Journal, Vol. 2, No. 2, 02.07.2007, p. 257-264.

Research output: Contribution to journalArticle

Kakei, Hiroyuki ; Tsuji, Riichiro ; Ohshima, Takashi ; Morimoto, Hiroyuki ; Matsunaga, Shigeki ; Shibasaki, Masakatsu. / Catalytic asymmetric epoxidation of α,β-unsaturated esters with chiral yttrium-biaryldiol complexes. In: Chemistry - An Asian Journal. 2007 ; Vol. 2, No. 2. pp. 257-264.
@article{1b4d4fe4894f46aeabbfdfc568cebc62,
title = "Catalytic asymmetric epoxidation of α,β-unsaturated esters with chiral yttrium-biaryldiol complexes",
abstract = "The full details of the asymmetric epoxidation of α,β- unsaturated esters catalyzed by yttrium complexes with biaryldiol ligands are described. An yttrium-biphenyldiol catalyst, generated from Y(OiPr) 3-biphenyldiol ligand-triphenylarsine oxide (1:1:1), is suitable for the epoxidation of various α,β-unsaturated esters. With this catalyst, β-aryl α,β-unsaturated esters gave high enantioselectivities and good yields (≤99{\%} ee). The reactivity of this catalyst is good, and the catalyst loading could be decreased to as little as 0.5-2 mol {\%} (the turnover number was up to 116), while high enantiomeric excesses were maintained. For β-alkyl α,β-unsaturated esters, an yttrium-binol catalyst, generated from Y-(OiPr)3-binol ligand-triphenylphosphine oxide (1:1:2), gave the best enantioselectivities (≤97{\%} ee). The utility of the epoxidation reaction was demonstrated in an efficient synthesis of (-)-ragaglitazar, a potential antidiabetes agent.",
author = "Hiroyuki Kakei and Riichiro Tsuji and Takashi Ohshima and Hiroyuki Morimoto and Shigeki Matsunaga and Masakatsu Shibasaki",
year = "2007",
month = "7",
day = "2",
doi = "10.1002/asia.200600309",
language = "English",
volume = "2",
pages = "257--264",
journal = "Chemistry - An Asian Journal",
issn = "1861-4728",
publisher = "John Wiley and Sons Ltd",
number = "2",

}

TY - JOUR

T1 - Catalytic asymmetric epoxidation of α,β-unsaturated esters with chiral yttrium-biaryldiol complexes

AU - Kakei, Hiroyuki

AU - Tsuji, Riichiro

AU - Ohshima, Takashi

AU - Morimoto, Hiroyuki

AU - Matsunaga, Shigeki

AU - Shibasaki, Masakatsu

PY - 2007/7/2

Y1 - 2007/7/2

N2 - The full details of the asymmetric epoxidation of α,β- unsaturated esters catalyzed by yttrium complexes with biaryldiol ligands are described. An yttrium-biphenyldiol catalyst, generated from Y(OiPr) 3-biphenyldiol ligand-triphenylarsine oxide (1:1:1), is suitable for the epoxidation of various α,β-unsaturated esters. With this catalyst, β-aryl α,β-unsaturated esters gave high enantioselectivities and good yields (≤99% ee). The reactivity of this catalyst is good, and the catalyst loading could be decreased to as little as 0.5-2 mol % (the turnover number was up to 116), while high enantiomeric excesses were maintained. For β-alkyl α,β-unsaturated esters, an yttrium-binol catalyst, generated from Y-(OiPr)3-binol ligand-triphenylphosphine oxide (1:1:2), gave the best enantioselectivities (≤97% ee). The utility of the epoxidation reaction was demonstrated in an efficient synthesis of (-)-ragaglitazar, a potential antidiabetes agent.

AB - The full details of the asymmetric epoxidation of α,β- unsaturated esters catalyzed by yttrium complexes with biaryldiol ligands are described. An yttrium-biphenyldiol catalyst, generated from Y(OiPr) 3-biphenyldiol ligand-triphenylarsine oxide (1:1:1), is suitable for the epoxidation of various α,β-unsaturated esters. With this catalyst, β-aryl α,β-unsaturated esters gave high enantioselectivities and good yields (≤99% ee). The reactivity of this catalyst is good, and the catalyst loading could be decreased to as little as 0.5-2 mol % (the turnover number was up to 116), while high enantiomeric excesses were maintained. For β-alkyl α,β-unsaturated esters, an yttrium-binol catalyst, generated from Y-(OiPr)3-binol ligand-triphenylphosphine oxide (1:1:2), gave the best enantioselectivities (≤97% ee). The utility of the epoxidation reaction was demonstrated in an efficient synthesis of (-)-ragaglitazar, a potential antidiabetes agent.

UR - http://www.scopus.com/inward/record.url?scp=34248189099&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=34248189099&partnerID=8YFLogxK

U2 - 10.1002/asia.200600309

DO - 10.1002/asia.200600309

M3 - Article

C2 - 17441160

AN - SCOPUS:34248189099

VL - 2

SP - 257

EP - 264

JO - Chemistry - An Asian Journal

JF - Chemistry - An Asian Journal

SN - 1861-4728

IS - 2

ER -