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

Authors

Wantanee Sittiwong, University of Nebraska - LincolnFollow
Michael W. Richardson, University of Nebraska-Lincoln
Charles E. Schiaffo, University of Nebraska - Lincoln
Thomas J. Fisher, University of Nebraska-LincolnFollow
Patrick Dussault, University of Nebraska-LincolnFollow

Date of this Version

2013

Citation

Beilstein J. Org. Chem. 2013, 9, 1526–1532.

Comments

© 2013 Sittiwong et al; licensee Beilstein-Institut.

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.