Rh-Catalyzed Aldehyde-Aldehyde Cross-Akdik Reaction under Base-Free Conditions : In Situ Aldehyde-Derived Enolate Formation through Orthogonal Activation
Rh-Catalyzed Aldehyde-Aldehyde Cross-Akdik Reaction under Base-Free Conditions : In Situ Aldehyde-Derived Enolate Formation through Orthogonal Activation
复制标题
无碱条件下 Rh 催化的醛-醛交叉 Akdik 反应：通过正交活化原位醛衍生烯醇化物形成
DOI：
10.1002/asia.201300928
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发表时间：
2013
期刊：
影响因子：
--
通讯作者：
Motomu Kanai
中科院分区：
文献类型：
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作者：
Luqing Lin;Kumiko Yamamoto;Shigeki Matsunaga;Motomu Kanai
描述了醛衍生的烯醇化物的化学选择性生成，以实现醛-乙醛交叉羟醛反应。一个组合的Rh/dippf系统有效地促进了异构化/羟醛序列，通过使用伯烯丙基，高烯丙基，和bishomoallylic醇;仲烯丙基和高烯丙基醇;和三烷氧基硼烷，衍生自伯烯丙基和高烯丙基醇。反应在环境温度下在无碱条件下进行，从而得到具有高化学选择性的交叉羟醛产物。机制的研究，以及它的应用双羟醛过程中的保护基团自由的条件下，也进行了描述。
The chemoselective generation of aldehyde‐derived enolates to realize an aldehydealdehyde cross‐aldol reaction is described. A combined Rh/dippf system efficiently promoted the isomerization/aldol sequence by using primary allylic, homoallylic, and bishomoallylic alcohols; secondary allylic and homoallylic alcohols; and trialkoxyboranes that were derived from primary allylic and homoallylic alcohols. The reaction proceeded at ambient temperature under base‐free conditions, thus giving cross‐aldol products with high chemoselectivity. Mechanistic studies, as well as its application to double‐aldol processes under protecting‐group‐free conditions, are also described.