【摘要】 以 2 ,4-二氧代戊酸甲酯 ( 1 )和 1 ,5 -二甲基 -6-亚甲基环己烯 ( 2 )为原料 ,通过 [2 +2 ]光环加成和 retro-Benzilic acid重排 ,合成了具有螺 [4,5 ]癸烷结构的岩兰烷基本碳架的化合物 3 .用锌粉选择还原五元环上碳碳双键得螺环二酮 ( 4 ) ,对环外羰基实施保护并将环上酮基转化为亚甲基得到重要的合成前体 6,经与甲基溴化镁的格氏反应生成混合的标题化合物 .利用羟基和异氰酸苯酯的反应生成一对 N-苯基氨基甲酸酯异构体 ( 1 2 ) ,二者分离后经四氢铝锂还原 ,完成了螺环倍半萜 (± ) -茅苍术醇和 (± ) -沉香螺醇的全合成 .更多还原

【Abstract】 The basic framework of spiro \ decane was constructed by photo-cycloaddition of methyl 2,4-dioxopentanoate(1) to 1,5-dimethyl-6-methylenecyclohexene(2) and retro-benzilic acid rearrangement of the proto-\photocycloadduction to afford a spirocyclic compounds(3) having vetivan structure. The carbon-carbon double bond of the five-membered ring in compound 3 was selectively reduced by using zinc dust to give spirocyclic diketone 4. The exocyclic carbonyl group was protected and the cyclic ketone group was converted into methylene group to give important vetivan-type precursor 6. The title compound 11 as a mixture was obtained by Grignard reaction with methyl magnesium bromide. The phenylurethanes isomers 12,derived from compound 11 by reaction of hydroxyl group with phenylisocyonate,was isolated from each other. (±)-Hinesol and (±)-agarospirol were synthesized by reduction with lithium aluminum finally. This method shortened the synthetic line,simplified empirical processes and raised the overall yield in comparison with our preceding papers. [WT5HZ]更多还原