Substrate Specific Silver(I)-Catalyzed Cycloisomerization of Diene Involving Alkyl Rearrangements: Syntheses of 1,2,5,6-Tetrahydrocuminic Acid, <i>p</i>-Menth-3-en-7-ol, and <i>p</i>-Menth-3-en-7-al
作者:Fuyuhiko Inagaki、Mizuki Matsumoto、Shisen Hira、Chisato Mukai
DOI:10.1248/cpb.c17-00433
日期:——
The novel cationic Ag(I)-catalyzed cycloisomerization, which is associated with alkyl rearrangements, from dimethyl 2-allyl-2-prenylmalonate (1) to dimethyl 4-isopropylcyclohex-3-ene-1,1-dicarboxylate (2) has been developed. Derivatization from the diester 2 into the diol 3 and its X-ray crystallographic analysis determined the structure. The mechanisms of the novel reaction were investigated by isotopic
从2-烯丙基-2-异戊二烯丙二酸二甲酯(1)到4-异丙基环己-3-烯-1,1-二羧酸二甲酯(2)与烷基重排有关的新型阳离子Ag(I)催化的环异构化发达。从二酯2衍生为二醇3及其X射线晶体学分析确定了结构。通过同位素实验研究了这种新反应的机理,这支持了异常的烷基转移。此外,产物2用于三种天然产物的总合成,即1,2,5,6-四氢孜然酸(12),对-薄荷3-3-烯-7-醇(13)和对薄荷简短说明-3-zh-7-al(14)。