Re2O7-catalyzed reaction of hemiacetals and aldehydes with O-, S-, and C-nucleophiles

Wantanee Sittiwong, Michael W. Richardson, Charles E. Schiaffo, Thomas J. Fisher, Patrick H. Dussault

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

Re(VII) oxides catalyze the acetalization, monoperoxyacetalization, monothioacetalization and allylation of hemiacetals. The reactions, which take place under mild conditions and at low catalyst loadings, can be conducted using hemiacetals, the corresponding O-silyl ethers, and, in some cases, the acetal dimers. Aldehydes react under similar conditions to furnish good yields of dithioacetals. Reactions of hemiacetals with nitrogen nucleophiles are unsuccessful. 1,2-Dioxolan-3-ols (peroxyhemiacetals) undergo Re(VII)-promoted etherification but not allylation. Hydroperoxyacetals (1-alkoxyhydroperoxides) undergo selective exchange of the alkoxide group in the presence of either Re2O7 or a Brønsted acid.

Original languageEnglish (US)
Pages (from-to)1526-1532
Number of pages7
JournalBeilstein Journal of Organic Chemistry
Volume9
DOIs
StatePublished - Jul 30 2013

Fingerprint

Allylation
Nucleophiles
Aldehydes
Acetals
Ethers
Dimers
Oxides
Nitrogen
Catalysts
Acids

Keywords

  • Allylation
  • Hemiacetal
  • O,O-acetal
  • O,S-thioacetal
  • Peroxyacetal
  • Re O
  • S,S-acetal

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Re2O7-catalyzed reaction of hemiacetals and aldehydes with O-, S-, and C-nucleophiles. / Sittiwong, Wantanee; Richardson, Michael W.; Schiaffo, Charles E.; Fisher, Thomas J.; Dussault, Patrick H.

In: Beilstein Journal of Organic Chemistry, Vol. 9, 30.07.2013, p. 1526-1532.

Research output: Contribution to journalArticle

Sittiwong, Wantanee ; Richardson, Michael W. ; Schiaffo, Charles E. ; Fisher, Thomas J. ; Dussault, Patrick H. / Re2O7-catalyzed reaction of hemiacetals and aldehydes with O-, S-, and C-nucleophiles. In: Beilstein Journal of Organic Chemistry. 2013 ; Vol. 9. pp. 1526-1532.
@article{4a7f35e28bea48888199714cc519e5f2,
title = "Re2O7-catalyzed reaction of hemiacetals and aldehydes with O-, S-, and C-nucleophiles",
abstract = "Re(VII) oxides catalyze the acetalization, monoperoxyacetalization, monothioacetalization and allylation of hemiacetals. The reactions, which take place under mild conditions and at low catalyst loadings, can be conducted using hemiacetals, the corresponding O-silyl ethers, and, in some cases, the acetal dimers. Aldehydes react under similar conditions to furnish good yields of dithioacetals. Reactions of hemiacetals with nitrogen nucleophiles are unsuccessful. 1,2-Dioxolan-3-ols (peroxyhemiacetals) undergo Re(VII)-promoted etherification but not allylation. Hydroperoxyacetals (1-alkoxyhydroperoxides) undergo selective exchange of the alkoxide group in the presence of either Re2O7 or a Br{\o}nsted acid.",
keywords = "Allylation, Hemiacetal, O,O-acetal, O,S-thioacetal, Peroxyacetal, Re O, S,S-acetal",
author = "Wantanee Sittiwong and Richardson, {Michael W.} and Schiaffo, {Charles E.} and Fisher, {Thomas J.} and Dussault, {Patrick H.}",
year = "2013",
month = "7",
day = "30",
doi = "10.3762/bjoc.9.174",
language = "English (US)",
volume = "9",
pages = "1526--1532",
journal = "Beilstein Journal of Organic Chemistry",
issn = "1860-5397",
publisher = "Beilstein-Institut Zur Forderung der Chemischen Wissenschaften",

}

TY - JOUR

T1 - Re2O7-catalyzed reaction of hemiacetals and aldehydes with O-, S-, and C-nucleophiles

AU - Sittiwong, Wantanee

AU - Richardson, Michael W.

AU - Schiaffo, Charles E.

AU - Fisher, Thomas J.

AU - Dussault, Patrick H.

PY - 2013/7/30

Y1 - 2013/7/30

N2 - Re(VII) oxides catalyze the acetalization, monoperoxyacetalization, monothioacetalization and allylation of hemiacetals. The reactions, which take place under mild conditions and at low catalyst loadings, can be conducted using hemiacetals, the corresponding O-silyl ethers, and, in some cases, the acetal dimers. Aldehydes react under similar conditions to furnish good yields of dithioacetals. Reactions of hemiacetals with nitrogen nucleophiles are unsuccessful. 1,2-Dioxolan-3-ols (peroxyhemiacetals) undergo Re(VII)-promoted etherification but not allylation. Hydroperoxyacetals (1-alkoxyhydroperoxides) undergo selective exchange of the alkoxide group in the presence of either Re2O7 or a Brønsted acid.

AB - Re(VII) oxides catalyze the acetalization, monoperoxyacetalization, monothioacetalization and allylation of hemiacetals. The reactions, which take place under mild conditions and at low catalyst loadings, can be conducted using hemiacetals, the corresponding O-silyl ethers, and, in some cases, the acetal dimers. Aldehydes react under similar conditions to furnish good yields of dithioacetals. Reactions of hemiacetals with nitrogen nucleophiles are unsuccessful. 1,2-Dioxolan-3-ols (peroxyhemiacetals) undergo Re(VII)-promoted etherification but not allylation. Hydroperoxyacetals (1-alkoxyhydroperoxides) undergo selective exchange of the alkoxide group in the presence of either Re2O7 or a Brønsted acid.

KW - Allylation

KW - Hemiacetal

KW - O,O-acetal

KW - O,S-thioacetal

KW - Peroxyacetal

KW - Re O

KW - S,S-acetal

UR - http://www.scopus.com/inward/record.url?scp=84885048218&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84885048218&partnerID=8YFLogxK

U2 - 10.3762/bjoc.9.174

DO - 10.3762/bjoc.9.174

M3 - Article

C2 - 23946852

AN - SCOPUS:84885048218

VL - 9

SP - 1526

EP - 1532

JO - Beilstein Journal of Organic Chemistry

JF - Beilstein Journal of Organic Chemistry

SN - 1860-5397

ER -