Synthesis and Reactivity of Weiss Diketone Derivative Bearing Four Phenylsulfanyl Groups
Synthesis and Reactivity of Weiss Diketone Derivative Bearing Four Phenylsulfanyl Groups
复制标题
四苯硫基Weiss二酮衍生物的合成及反应活性
DOI：
10.1002/ejoc.202201029
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发表时间：
2022
影响因子：
2.8
通讯作者：
Fukazawa Aiko
中科院分区：
文献类型：
--
作者：
Yasui Kosuke;Isogai Ryosuke;Fukazawa Aiko
合成了一种在羰基对角线α-位带有4个苯硫基的双环[3.3.0]辛烷-3，7-二酮，作为探索对称韦斯二酮区域选择性转化的关键中间体.四-PhS-取代的双环[3.3.0]辛烷-3，7-二酮通过在PhSSO 2 Ph存在下使用LDA使韦斯二酮去质子化来制备。由此获得的四-PhS-取代的衍生物用作进一步区域选择性碱促进的烯醇化的支架。此外，四-PhS-取代的韦斯二酮经历了意想不到的碱促进的重排，通过PhS基团的迁移形成异构的四-PhS-取代的双环[3.3.0]辛烷-3，7-二酮，可能是通过中断的Favorskii重排。
A bicyclo[3.3.0]octane‐3,7‐dione, bearing four phenylsulfanyl (PhS) groups at the diagonalα‐positions of the carbonyls, was synthesized as a key intermediate useful for exploring the regioselective transformations of symmetrical Weiss diketone. Tetra‐PhS‐substituted bicyclo[3.3.0]octane‐3,7‐dione was prepared by deprotonation of the Weiss diketone, using LDA in the presence of PhSSO2Ph. The tetra‐PhS‐substituted derivative thus obtained served as a scaffold for further regioselective base‐promoted enolization. Furthermore, the tetra‐PhS‐substituted Weiss diketone underwent an unexpected base‐promoted rearrangement to form isomeric tetra‐PhS‐substituted bicyclo[3.3.0]octane‐3,7‐dione through migration of PhS groups, likely through an interrupted Favorskii rearrangement.