TOTAL SYNTHESIS OF (+)-COLLETODIOL - NEW METHODOLOGY FOR THE SYNTHESIS OF MACROLACTONES
TOTAL SYNTHESIS OF (+)-COLLETODIOL - NEW METHODOLOGY FOR THE SYNTHESIS OF MACROLACTONES
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DOI：
10.1021/jo00265a033
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发表时间：
1989-02-17
影响因子：
3.6
通讯作者：
WILEY, MR
中科院分区：
文献类型：
--
作者：
KECK, GE;BODEN, EP;WILEY, MR
本文详细介绍了两种不同结构的大环双（内酯）醇的合成方法。对不正确结构（C11 epi）的初始方法依赖于甲基α的操纵。-D-glucopyranoside为C11 epi结构的C8-C14段设定所需的立体化学。第二种方法是在基于x射线晶体学证据的结构修正后开始的，采用Lewis酸介导的烯丙基锡烷33加成到。β。-烷氧醛34设定C8-C14亚基的立体化学。该路线采用了许多专门针对该问题开发的新合成反应，在9个线性操作中得到(-)-烟碱二醇，总收率为8.2%。
Synthetic efforts directed toward two different structures suggested for the macrocylic bis(lactone) colletodiol are detailed. The initial approach to an incorrect structure (C11 epi) relies upon the manipulation of methyl .alpha.-D-glucopyranoside to set the required stereochemistry for the C8-C14 segment of the C11 epi structure. The second approach, initiated after structural revision based upon X-ray crystallographic evidence, employs a Lewis acid mediated addition of allylstannane 33 to .beta.-alkoxy aldehyde 34 to set the stereochemistry of the C8-C14 subunit. This route, which employs a number of new synthetic reactions developed specifically for this problem, gives (-)-colletodiol in nine linear operations and 8.2% overall yield.