Stereoselective Synthesis of the C1-C29 Part of Amphidinol 3
Stereoselective Synthesis of the C1-C29 Part of Amphidinol 3
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DOI：
10.1021/jo502322m
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发表时间：
2015-01-16
影响因子：
3.6
通讯作者：
Oishi, Tohru
中科院分区：
文献类型：
--
作者：
Tsuruda, Takeshi;Ebine, Makoto;Oishi, Tohru
实现了两苯胺醇3 （AM3）的C1-C29部分的立体选择性合成。C1-C20部分由三个构建块通过区域选择性交叉复分解形成C4-C5双键，并在两个Weinreb酰胺中加入一个烯基锂和一个乙酰化锂，然后分别进行不对称还原形成C9-C10和C14-C15键。通过连续交叉复分解和oxa-Michael加成序列合成C21-C29部分，构建C25和C27上的1,3-二醇体系，并通过Brown不对称丁基化引入C23和C24上的立体中心。C1-C20和C21-C29部分的耦合是通过Julia-Kocienski烯烃和C20-C21双键在C4-C5和C8-C9双键存在下的区域和立体选择性二羟基化来实现的，从而得到AM3的C1-C29部分。
Stereoselective synthesis of the C1-C29 part of amphidinol 3 (AM3) was achieved. The C1-C20 part was assembled from three building blocks via regioselective cross metathesis to form the C4-C5 double bond and addition of an alkenyllithium and a lithium acetylide to two Weinreb amides followed by asymmetric reduction to form the C9-C10 and C14-C15 bonds, respectively. The C21-C29 part was synthesized via successive cross metathesis and oxa-Michael addition sequence to construct the 1,3-diol system at C25 and C27 and Brown asymmetric crotylation to introduce the stereogenic centers at C23 and C24. Coupling of the C1-C20 and C21-C29 parts was achieved by Julia-Kocienski olefination and regio- and stereoselective dihydroxylation of the C20-C21 double bond in the presence of the C4-C5 and C8-C9 double bonds to afford the C1-C29 part of AM3.