Catalytic Alkynylation of Cyclic Acetals and Ketals Enabled by Synergistic Gold(I)/Trimethylsilyl Catalysis

M. Berthet (1) , O. Songis (1) , C. Taillier (1) , V. Dalla (1)

1 URCOM - Unité de Recherche en Chimie Organique et Macromoléculaire

A completely regioselective and challenging gold(I)-catalyzed ring-opening of cyclic 1,3-dioxolanes and dioxanes by trimethylsilyl alkynes to set diol-derived propargyl trimethylsilyl bis-ethers is reported. This unprecedented and not trivial transformation does not operate with the catalytic methodologies recently reported for catalytic alkynylation of acyclic acetals/ketals, and is uniquely enabled by the application of a recently introduced synergistic gold(I)-silicon catalysis concept capable of producing simultaneously catalytic amounts of two key players, a silicon-based Lewis superacid and a nucleophilic gold acetylide. © 2017 American Chemical Society.

Keywords: Ethers; 3-Dioxolanes; Alkynylations; Catalytic amounts; Cyclic acetals; Gold acetylide; Regio-selective; Silicon-based; Trimethylsilyl; 1; 3 dioxolane; acetal derivative; dioxane derivative; gold; Lewis acid; nucleophile; silicon; trimethylsilyl derivative; alkynylation; Article; catalysis; catalyst; quantum yield; reaction analysis; reaction optimization; regioselectivity; ring opening; stereochemistry

Domains: Chemical Sciences

M. Berthet, O. Songis, C. Taillier, V. Dalla. Catalytic Alkynylation of Cyclic Acetals and Ketals Enabled by Synergistic Gold(I)/Trimethylsilyl Catalysis. Journal of Organic Chemistry, 2017, 82 (18), pp.9916-9922. ⟨10.1021/acs.joc.7b01828⟩. ⟨hal-02413280⟩