New Syntetic Methods by use of Organic Sulfur and Selenium

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We have studied of the scope and limitations of Se-phenyl (selenothioperoxy) benzoates 1 (S-acyl Se-phenyl selenosulfides) as useful organic synthetic reagents and found the following intersting results.i) Selenosulfide 1 could be used as a mild acylating agent of an amino group. Maytenin was convenientyl synthesized from spermidin.ii) Radical reactions of olefins with 1 gave addition products. A characteristic reaction feature of these radical reactions was shown in that all the additions occurred regioselectiveyy in anti-@markownikoff manner as for the phenylseleno group.iii) Seleno-substituted thiahomoprotoadamantanone was prepared by the intramolecular radical cyclization. An unexpected transformation to the vinyl selenide was observed by oxidation of the seleno group of the thiahomoprotoadmantanone.iv) The radical reaction of 1 with allyltin compounds gave allyl thiobenzoate, whereas vinyltin compounds gave either an adduct or a vinyl thiobenzoate depending on the substituent on the starting vinyltins.v) A new method of regioselective oxyselenenylation was accomplished by oxymercuration of an olefin and subsequent selenenylation by 1 vai a free-radical process. Furthermore, the above reaction led to a novel selenocyclization reaction by use of an <alpha>,<beta>-unsaturated ester bearing a terminal olefin as a starting substrate.