New Syntetic Methods by use of Organic Sulfur and Selenium

我们研究了硒苯基（硒硫过氧）苯甲酸盐1 （s -酰基硒苯基硫化物）作为有用的有机合成试剂的范围和局限性，发现了以下有趣的结果。i)硫代硒1可用作氨基的温和酰化剂。以亚精精素为原料，方便地合成了玫婷素。烯烃与1的自由基反应生成加成产物。这些自由基反应的一个特征是，苯硒基的加成均以anti-@markownikoff的方式选择性地发生。iii)采用分子内自由基环化法制备了硒取代的噻吩原金刚烷酮。通过氧化硫同原甾酮的硒基，观察到意想不到的乙烯基硒化转化。iv) 1与烯丙基锡化合物的自由基反应生成烯丙基硫苯甲酸酯，而乙烯基锡化合物根据起始乙烯基的取代基生成加合物或乙烯基硫苯甲酸酯。(5)提出了一种区域选择性氧亚硒化的新方法，即烯烃的氧汞化反应和随后的自由基亚硒化反应。此外，上述反应导致了一个新的硒化反应，该反应使用< α >,< β >-不饱和酯，末端烯烃作为起始底物。

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.