The mechanism of the catalysis of the reversible (propargyl ester)/(allenyl ester) rearrangement (10 ⇄ 11) by silver(I) ions was investigated, using optically active and diastereoisomeric esters as well as 14 C- and 18 O-labelling. ... The rate-determining step of the (propargyl ester)/(allenyl ester) rearrangement (10 ⇄ 11) occurs in a silver(I) complex with the substrates (10, 11), which is formed in a pre-equilibrium. This follows from kinetic experiments (cf. Fig. 6, 7, 8, 10) ...
