Regio‐ and Stereoselective Intermolecular Hydroalkoxylation of Alkynes Catalysed by Cationic Gold(I) Complexes

Vinyl ethers and ketals are obtained from the reaction of phenylacetylene derivatives and dimethyl acetylenedicarboxylate (DMAD) with alcohols in good yields and levels of stereoselectivity by using cationic gold(I)‐phosphine complexes as catalysts. By choosing the appropriate phosphine, the selective formation of the Z or the E isomer of the vinyl ether can be tuned, and the undesired formation of the ketal can be controlled. The isomerisation of fumarates ( Z ‐isomer) to maleates ( E ‐isomer) is a gold‐catalysed process that can be conducted in one‐pot. When using polyols, 5‐membered cyclic ketals are easily isolated by extraction with hexane and the gold complex can be reused.