Methoxycarbonyl mercuric acetate

Jack Halpern I want to ask Dr. Dessy two questions. Sometime ago we looked at substantially the same reaction (i.e., decomposition of methoxycarbonyl mercuric acetate) in aqueous solution, and we found also that this decomposition is catalyzed by hydrogen ion and by chloride ion. The rate is first-order in (H+), but we found that in addition to a path first-order in (Cl-) there were also appreciable contributions from higher order paths, certainly second-order and possibly also third. This implies that the process is further aided by coordination of more than one halide to the metal. I wondered whether there were any corresponding indications in these solvent systems. 

Cyclization by amidomercuration has been reported (391). Reaction of N-methoxycarbonyl-6-aminohept-l-ene (211) with mercuric acetate gave the organomercurial (212). Reductive coupling of 212 with l-decen-3-one in the usual way gave the cis and trans isomers (213). Successive treatment of 213 with ethanedithiol, Raney nickel, and ethanolic hydrogen chloride afforded ( )-sole-nopsin A (Id, 2 parts) and its isomer (Ic, 3 parts), which were separable by preparative gas chromatography (GC) (Scheme 5) (391). 

Chart II. Mercuric acetate oxidation of dihydrooleavamine and methoxycarbonyl dihydrooleavamine. 

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