Highly reactive and selective olefin carbometalation

高反应性和选择性的烯烃碳金属化

基本信息

批准号：
08454196
负责人：
NAKAMURA Eiichi
金额：
$ 4.8万
依托单位：
The University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1996
资助国家：
日本
起止时间：
1996 至 1997
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08454196/
关键词：
allyl metal hydrazone carbometalation organocuprate computational study asymmetric synthesis

项目摘要

Addition of an organometallic reagent to an isolated olefin (olefin carbometalation reaction) is not only of synthetic interest but of mechanistic interest. Although the organometallic addition of carbonyl compounds has been a well-established chemistry, the olefin carbometalation reaction has been developed in rather limited araea owing to the lack of substantial p information on the reaction mechanism of the carbometalation reaction. In this reset, we developed new carbometalation reactions by using highly reactive and selective reagents. The experimental and theoretical results are listed below.(1) Theoretical studies on the addition of polymetallic lithium organocuprate clusters to C-Cmultiple bonds was carried out with ab initio and density functional calculation. This study firstly provided detailed mechanisms of carfbocupration and 1,4-addition reaction, and revealed importance of cluster structure of the reagent.(2) Highly enantioselective addition of organometallic reagent to C=N double bond was achieved by using optically active allylic zinc reagents which were developed during the study on enantioselective carbometalation reaction of an isolated olefin.(3) Addition of metal enolate species to cyclopropenone acetal have been found in the course of the study on the olefin carbometalation reaction. The carbometalation product, cyclopropyl metal, was trapped by various electrophile. This is the first example of the addition of metal enolate to olefin and utilization of the intermediate organometallic species.

将有机金属试剂添加到分离的烯烃中（烯烃碳金属化反应）不仅具有合成意义，而且具有机械意义。尽管羰基化合物的有机金属加成已经是一种成熟的化学反应，但由于缺乏关于碳金属化反应机理的大量信息，烯烃碳金属化反应的发展领域相当有限。在这次重置中，我们通过使用高反应性和选择性试剂开发了新的碳金属化反应。实验和理论结果如下： (1)利用从头计算和密度泛函计算方法，对多金属有机铜酸锂团簇在C-C多重键上的加成进行了理论研究。本研究首次详细阐述了碳铜化和1,4-加成反应的机理，并揭示了试剂簇结构的重要性。(2)利用光学活性烯丙基锌试剂实现了有机金属试剂与C=N双键的高度对映选择性加成。 (3)在环丙烯酮缩醛中发现了金属烯醇化物的加成反应。烯烃碳金属化反应的研究过程。碳金属化产物环丙基金属被各种亲电子试剂捕获。这是将金属烯醇化物添加到烯烃中并利用中间有机金属物质的第一个例子。