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36.1.4.1.2 Variation 2: Using Mercury(II) Acetate–Sodium Trithiocarbonate

DOI: 10.1055/sos-SD-036-00146

Russell, A. T.Science of Synthesis, (200836201.

Sulfides and thiosulfates react rapidly with organomercury(II) salts but, in general, the products are unstable and tend to lead to retro-oxymercuration with regeneration of the alkene. However, in the case of α,β-unsaturated esters and acids, following mercuration, immediate demercuration to yield the alcohol or alkoxy derivative occurs on treatment with, for example, hydrogen sulfide.[‌2‌] This mild demercuration method is not widely applied but has found application with the two classes of substrate mentioned above and has been found to deliver demercuration with predominantly retention of configuration under certain conditions. For example, highly stereoselective hydration of tiglic acid 36 (R1=H) gives erythro-37 (R1=H) (sodium borohydride mediated demercuration delivers a 1:1 mixture of diastereomers) (Scheme 12).[‌75‌] The regiochemistry of the hydroxylation fits with ring opening of a positively charged intermediate and should be contrasted with the manganese-based protocol in Section 36.1.4.3.

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