Chiral hydroperoxides as oxygen source in the catalytic stereoselective epoxidation of allylic alcohols by sandwich-type polyoxometalates

Control of enantioselectivity through a metal-coordinated template

Waldemar Adam, Paul L. Alsters, Ronny Neumann, Chantu R. Saha-Möller, Dieter Seebach, Albert K. Beck, Rui Zhang

Research output: Contribution to journalArticle

63 Citations (Scopus)

Abstract

The epoxidation of allylic alcohols is shown to be efficiently and selectively catalyzed by the oxidatively resistant sandwich-type polyoxometalates, POMs, namely [WZnM2(ZnW9O 34)2]q- [M = OV(IV), Mn(II), Ru(III), Fe(III), Pd(II), Pt(II), Zn(II); q = 10-12], with organic hydroperoxides as oxygen source. Conspicuous is the fact that the nature of the transition metal M in the central ring of polyoxometalate affects significantly the reactivity, chemoselectivity, regioselectivity, and stereoselectivity of the allylic alcohol epoxidation. For the first time, it is demonstrated that the oxovanadium(IV)-substituted POM, namely [ZnW(VO)2(ZnW 9O34)2]12-, is a highly chemoselective, regioselective, and also stereoselective catalyst for the clean epoxidation of allylic alcohols. A high enantioselectivity (er values up to 95:5) has been achieved with [ZnW(VO)2(ZnW9O 34)2]12- and the sterically demanding TADOOL-derived hydroperoxide TADOOH as regenerative chiral oxygen source. Thus, a POM-catalyzed asymmetric epoxidation of excellent catalytic efficiency (up to 42 000 TON) has been made available for the development of sustainable oxidation processes. The high reactivity and selectivity of this unprecedented oxygen-transfer process are mechanistically rationalized in terms of a peroxy-type vanadium(V) template.

Original languageEnglish
Pages (from-to)8222-8231
Number of pages10
JournalJournal of Organic Chemistry
Volume68
Issue number21
DOIs
Publication statusPublished - Oct 17 2003

Fingerprint

Epoxidation
Enantioselectivity
Hydrogen Peroxide
Metals
Oxygen
Stereoselectivity
Regioselectivity
Vanadium
Transition metals
Oxidation
Catalysts
allyl alcohol

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Chiral hydroperoxides as oxygen source in the catalytic stereoselective epoxidation of allylic alcohols by sandwich-type polyoxometalates : Control of enantioselectivity through a metal-coordinated template. / Adam, Waldemar; Alsters, Paul L.; Neumann, Ronny; Saha-Möller, Chantu R.; Seebach, Dieter; Beck, Albert K.; Zhang, Rui.

In: Journal of Organic Chemistry, Vol. 68, No. 21, 17.10.2003, p. 8222-8231.

Research output: Contribution to journalArticle

@article{8a674a3d90aa4490a5af7c193dab8e83,
title = "Chiral hydroperoxides as oxygen source in the catalytic stereoselective epoxidation of allylic alcohols by sandwich-type polyoxometalates: Control of enantioselectivity through a metal-coordinated template",
abstract = "The epoxidation of allylic alcohols is shown to be efficiently and selectively catalyzed by the oxidatively resistant sandwich-type polyoxometalates, POMs, namely [WZnM2(ZnW9O 34)2]q- [M = OV(IV), Mn(II), Ru(III), Fe(III), Pd(II), Pt(II), Zn(II); q = 10-12], with organic hydroperoxides as oxygen source. Conspicuous is the fact that the nature of the transition metal M in the central ring of polyoxometalate affects significantly the reactivity, chemoselectivity, regioselectivity, and stereoselectivity of the allylic alcohol epoxidation. For the first time, it is demonstrated that the oxovanadium(IV)-substituted POM, namely [ZnW(VO)2(ZnW 9O34)2]12-, is a highly chemoselective, regioselective, and also stereoselective catalyst for the clean epoxidation of allylic alcohols. A high enantioselectivity (er values up to 95:5) has been achieved with [ZnW(VO)2(ZnW9O 34)2]12- and the sterically demanding TADOOL-derived hydroperoxide TADOOH as regenerative chiral oxygen source. Thus, a POM-catalyzed asymmetric epoxidation of excellent catalytic efficiency (up to 42 000 TON) has been made available for the development of sustainable oxidation processes. The high reactivity and selectivity of this unprecedented oxygen-transfer process are mechanistically rationalized in terms of a peroxy-type vanadium(V) template.",
author = "Waldemar Adam and Alsters, {Paul L.} and Ronny Neumann and Saha-M{\"o}ller, {Chantu R.} and Dieter Seebach and Beck, {Albert K.} and Rui Zhang",
year = "2003",
month = "10",
day = "17",
doi = "10.1021/jo034923z",
language = "English",
volume = "68",
pages = "8222--8231",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "21",

}

TY - JOUR

T1 - Chiral hydroperoxides as oxygen source in the catalytic stereoselective epoxidation of allylic alcohols by sandwich-type polyoxometalates

T2 - Control of enantioselectivity through a metal-coordinated template

AU - Adam, Waldemar

AU - Alsters, Paul L.

AU - Neumann, Ronny

AU - Saha-Möller, Chantu R.

AU - Seebach, Dieter

AU - Beck, Albert K.

AU - Zhang, Rui

PY - 2003/10/17

Y1 - 2003/10/17

N2 - The epoxidation of allylic alcohols is shown to be efficiently and selectively catalyzed by the oxidatively resistant sandwich-type polyoxometalates, POMs, namely [WZnM2(ZnW9O 34)2]q- [M = OV(IV), Mn(II), Ru(III), Fe(III), Pd(II), Pt(II), Zn(II); q = 10-12], with organic hydroperoxides as oxygen source. Conspicuous is the fact that the nature of the transition metal M in the central ring of polyoxometalate affects significantly the reactivity, chemoselectivity, regioselectivity, and stereoselectivity of the allylic alcohol epoxidation. For the first time, it is demonstrated that the oxovanadium(IV)-substituted POM, namely [ZnW(VO)2(ZnW 9O34)2]12-, is a highly chemoselective, regioselective, and also stereoselective catalyst for the clean epoxidation of allylic alcohols. A high enantioselectivity (er values up to 95:5) has been achieved with [ZnW(VO)2(ZnW9O 34)2]12- and the sterically demanding TADOOL-derived hydroperoxide TADOOH as regenerative chiral oxygen source. Thus, a POM-catalyzed asymmetric epoxidation of excellent catalytic efficiency (up to 42 000 TON) has been made available for the development of sustainable oxidation processes. The high reactivity and selectivity of this unprecedented oxygen-transfer process are mechanistically rationalized in terms of a peroxy-type vanadium(V) template.

AB - The epoxidation of allylic alcohols is shown to be efficiently and selectively catalyzed by the oxidatively resistant sandwich-type polyoxometalates, POMs, namely [WZnM2(ZnW9O 34)2]q- [M = OV(IV), Mn(II), Ru(III), Fe(III), Pd(II), Pt(II), Zn(II); q = 10-12], with organic hydroperoxides as oxygen source. Conspicuous is the fact that the nature of the transition metal M in the central ring of polyoxometalate affects significantly the reactivity, chemoselectivity, regioselectivity, and stereoselectivity of the allylic alcohol epoxidation. For the first time, it is demonstrated that the oxovanadium(IV)-substituted POM, namely [ZnW(VO)2(ZnW 9O34)2]12-, is a highly chemoselective, regioselective, and also stereoselective catalyst for the clean epoxidation of allylic alcohols. A high enantioselectivity (er values up to 95:5) has been achieved with [ZnW(VO)2(ZnW9O 34)2]12- and the sterically demanding TADOOL-derived hydroperoxide TADOOH as regenerative chiral oxygen source. Thus, a POM-catalyzed asymmetric epoxidation of excellent catalytic efficiency (up to 42 000 TON) has been made available for the development of sustainable oxidation processes. The high reactivity and selectivity of this unprecedented oxygen-transfer process are mechanistically rationalized in terms of a peroxy-type vanadium(V) template.

UR - http://www.scopus.com/inward/record.url?scp=0142121745&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0142121745&partnerID=8YFLogxK

U2 - 10.1021/jo034923z

DO - 10.1021/jo034923z

M3 - Article

VL - 68

SP - 8222

EP - 8231

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 21

ER -