With Acyl as Migrating Groups

3]-SIGMATROPIC REARRANGEMENTS 3.4.1 With Acyl as Migrating Groups 

The first nonambiguous report of rearrangement of esters derived from propargyl alcohols promoted by silver salts was due to Saucy and coworkers at Hoffmann-La Roche.50 Their observations on the transformation of acetate derived from 

Further mechanistic work with optically active and labeled compounds confirmed that the rate-determining step in such rearrangement was the silver coordination to the alkyne moiety and revealed that the silver-catalyzed allene epimerization was 2-40 times faster than the propargyl ester rearrangement.53 

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