Summary. New catalytic systems have been found which effect the isomerization of cc- acetylenic alcohols to the corresponding a,P-unsaturated carbonyl compounds with high efficiency. These are combinations of silylvanadates with silanols or silanediols. ... Rearrangements of esterified acetylenic alcohols, however, proceed in high yield in the presence of certain transition metals [9] in charge induced [3s, 3s]-sigmatropic reactions [ l O j [ll], and the intermediates ...