Highly reactive and selective olefin carbometalation

将有机金属试剂添加到分离的烯烃中（烯烃碳化反应）不仅具有合成意义，而且具有机理意义。虽然羰基化合物的有机金属加成反应已经是一种成熟的化学反应，但由于缺乏有关碳酰化反应机理的大量信息，烯烃碳酰化反应的研究领域相当有限。在这个重置中，我们通过使用高反应性和选择性试剂开发了新的碳化反应。下面列出了实验和理论结果。(1)采用从头算和密度泛函方法研究了多金属有机铜酸锂簇合物对C-C多重键的加成反应。本研究首次提供了详细的羰基铜化反应和1，4-加成反应机理，揭示了试剂团簇结构的重要性。(2)利用在烯烃不对称羰化反应研究中开发的光学活性烯丙基锌试剂，实现了有机金属试剂对C=N双键的高不对称加成反应。(3)在烯烃碳化反应的研究过程中，发现了金属烯醇化物对环丙烯酮缩醛的加成反应。碳化产物环丙基金属被各种亲电试剂捕获。这是将金属烯醇化物加成到烯烃上并利用中间体有机金属物质的第一个实例。

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.