鲨鱼驱避剂帕沃宁-4的合成。
Synthesis of the shark repellent pavoninin-4.
作者信息
Williams John R, Gong Hua, Hoff Nathan, Olubodun Olaoluwa I
机构信息
Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122-2585, USA.
出版信息
J Org Chem. 2005 Dec 23;70(26):10732-6. doi: 10.1021/jo051733a.
[reaction: see text] The first synthesis of the shark repellent pavoninin-4, 3, was achieved in 12 steps with 21% overall yield from diosgenin, 8. Key reactions involve an efficient synthesis of the C-15alpha hydroxyl steroid from a C-16beta hydroxyl steroid by an unexpected 1,2-transposition strategy, a stereospecific glycosylation of a hindered C-15alpha alcohol using glycosyl fluoride as a glycosyl donor and a highly chemoselective acetylation of the C-26 primary alcohol by catalytic transesterification.
[反应：见正文] 鲨鱼驱避剂帕沃宁-4（3）的首次全合成以薯蓣皂苷元为起始原料，经过12步反应完成，总收率为21%。关键反应包括通过意外的1,2-转位策略从C-16β羟基甾体高效合成C-15α羟基甾体，使用氟代糖作为糖基供体对受阻的C-15α醇进行立体选择性糖基化，以及通过催化酯交换对C-26伯醇进行高度化学选择性乙酰化。 8
Zotero 插件