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The /3-carbon of ,/3-unsaturated ketones, esters, lactones, and nitriles can be oxidatively functionalized in a regiospecific manner in a simple sequence of reactions. Michael addition of thiophenol followed by oxidation with jV-chlorosuccinimide gives chloro sulfides that readily lose HC1 to give 3-phenylthio enones, acrylates, and other vinyl derivatives.

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ferent time intervals aliquots (4 ml) were withdrawn (under argon) and the resin separated immediately by suction filtration, washed thoroughly with DMF, CH2CI2, and MeOH, and then subjected to amino acid analysis. The rate of decrease in amino acid content was taken as the rate of photolysis of the -methylphenacyl ester anchoring bond. Exactly the same experiments were performed on tetrapeptide resins VII and VIII to determine the rate of photolytic cleavage of the o-nitrobenzyl and benzyl ester linkages. The results are summarized in Figure 1. For the studies of the rates of acidolysis or hydrazinolysis of the resins III, VII, and VIII, 0.5 g each of the samples were stirred individually in 20 volumes each of TFA-CH2CI2 (1:1) or 10% H2NNH2 (DMF) in six separate flasks. Aliquots (1 ml) from each reaction were taken at different times and treated as described above for the photolysis experiments. The results are also shown in Figure 1.