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Updated: Jul 7, 2026

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols
Published on: April 4, 2014
Three-component coupling reaction and cyclization of N-tosylimines and TMS-substituted propiolate mediated by DABCO
Yuji Matsuya1, Kousuke Hayashi, Akiho Wada
1Graduate School of Medicine and Pharmaceutical Sciences, University of Toyama, 2630 Sugitani, Toyama 930-0194, Japan.
Abstract:
A new three-component coupling reaction of methyl 3-trimethylsilylpropiolate, N-tosylimine, and tosylamide mediated by DABCO was developed. This reaction was based on the consecutive alpha- and beta-activation method of propiolate involving intramolecular silyl migration previously developed by our group. On the basis of these results, a new cyclization reaction was designed to find a chromene-forming reaction utilizing salicyl N-tosylimine as a bifunctional substrate.
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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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