Synthesis of a C(1)-C(14)-containing fragment-of callipeltoside A
Synthesis of a C(1)-C(14)-containing fragment-of callipeltoside A
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DOI：
10.1021/ol9906514
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发表时间：
1999-07-15
期刊：
影响因子：
5.2
通讯作者：
Zhao, HY
中科院分区：
文献类型：
--
作者：
Hoye, TR;Zhao, HY
通过醛2和酮酯3之间的二价阴离子羟醛偶联反应有效地合成了callipeltoside A的含C（1）-C（14）的片段（1，方案1）。在13中的烯烃和Grubbs引发剂15之间令人惊讶地缺乏反应性。发现了15与烯丙醇（烷-1-烯-3-醇）之间的反应以及它们随后裂解成甲基酮的同样令人惊讶的速率加速。原位H-1 NMR分析已被证明是一个非常有用的工具，用于监测复杂的底物，如13的RCM反应。
[GRAPHICS]A C(1)-C(14)-containing fragment of callipeltoside A (1, Scheme 1) was synthesized efficiently via a dianion aldol coupling reaction between aldehyde 2 and ketoester 3, A surprising lack of reactivity between the alkenes in 13 and the Grubbs initiator 15 was encountered. An equally surprising rate acceleration of the reaction between 15 and allylic alcohols (alk-1-en-3-ols) as well as their subsequent cleavage to methyl ketones was discovered. In situ H-1 NMR analysis has proven to be a very useful tool for monitoring RCM reactions of complex substrates such as 13.