DEVELOPMENT AND SYNTHETIC APPLICATION FOR STEREOSELECTIVE MICHAEL/ALDOL TANDEM REACTION TRIGGERED BY THIOLATE ANION

硫醇阴离子引发的立体选择性迈克尔/醛醇串联反应的开发及合成应用

基本信息

批准号：
11640536
负责人：
KAMIMURA Akio
金额：
$ 2.62万
依托单位：
YAMAGUCHI UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2001
项目状态：
已结题

项目摘要

The titled reaction, the Michael/aldol tandem reaction, was investigated and found the following developments.1) We found this reaction can be applied to not only unsaturated esters but also unsaturated amides. Use of the procedure makes it easy to prepare amide-Baylis-Hillman adducts, which was difficult to synthesize under classical Baylis-Hillman reaction conditions. It should be mentioned that our reaction condition requires no special protection for the acidic amide NH proton for the progress of aldol reaction.2) Use of magnesium ion as a counter cation of thiolate opens the new aspect of the reaction that shows opposite diastereoselectivity for the aldol reaction. Under these conditions, anti-aldols, the preparation of which are recognized to be limited. We have also attempted to catch the reaction intermediate to understand the reaction mechanism, and found that a-thioalkoxide is the intermediate of the reaction.3) We have developed a new ready method to prepare multi-substituted tetrahydrofurans through the present method.4) Regiochemistry of radical elimination reaction was investigated. The regioselective transformation of the tandem adducts to α, β-unsaturated or β, γ-unsaturated ester was accomplished. This result is the first example of the regiocontrol in the radical elimination reaction.5) We have accomplished the first regiocontrol of the tandem or the Michael reaction of thiol to unsymmetrically substituted fumaric ester.

研究了标题的反应，迈克尔/藻串联反应，并发现了以下发展。1）我们发现该反应不仅可以应用于不饱和酯，还可以应用于不饱和酰胺。该过程的使用使得准备酰胺 - 贝里斯 - 希尔曼加合物变得容易，这很难在经典的Baylis-Hillman反应条件下合成。应该提到的是，我们的反应条件不需要特殊保护酸性酰胺NH质子来进行ADOL反应的进展。2）使用镁离子作为硫醇酯的反阳离子，打开了反应的新方面，该反应显示了ADOL反应的非映射性相反。在这些条件下，抗醛醇，其制剂被认为是有限的。我们还试图捕获反应中间体以了解反应机制，并发现A-甲烷氧化物是反应的中间体。3）我们已经开发了一种新的现成方法来通过目前的方法来制备多取代的四氢呋喃。完成了串联加合物对α，β-未饱和或β，γ-不饱和酯的调节转化。该结果是从根治性消除反应中进行的第一个例子。5）我们已经完成了串联的第一个统一控制或硫醇对未取代的富马酯的迈克尔反应。