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Updated: Dec 29, 2025

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols
Published on: April 4, 2014
Tandem Three-Component Synthesis of syn-1,2- and syn-1,3-Diol Derivatives
Keisuke Murata1, Hiroya Takeshita1, Keita Sakamoto1
1Department of Applied Chemistry Faculty of Science and Engineering, Chuo University, 1-13-27 Kasuga, Bunkyo-ku, Tokyo, 112-8551, Japan.
Abstract:
The development of efficient methods for stereocontrolled synthesis of polyol derivatives has been of continuing interest for the synthetic community. We describe herein tandem olefin cross-metathesis/hemiacetalization/intramolecular oxa-Michael addition of allylic/homoallylic alcohols, α,β-unsaturated ketones, and aldehydes, which enabled the synthesis of syn-1,2- and syn-1,3-diol derivatives in a step-economical manner. A series of differentially protected polyol derivatives could be obtained in subsequent transformations via chemoselective/regioselective cleavage of the acetal moiety of the tandem reaction products.
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The reaction begins with transferring a proton from the acid catalyst to one of the hydroxyl groups, producing an oxonium ion.
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