Highly reactive and selective olefin carbometalation

高反应性和选择性的烯烃碳金属化

• 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

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.

在分离的烯烃（烯烃碳测定反应）中添加有机金属试剂不仅具有合成的兴趣，而且具有机械意义。尽管羰基化合物的有机金属添加是一种公认​​的化学，但由于缺乏有关碳测量反应反应机理的大量信息，因此在有限的ARAEA中开发了烯烃碳测定反应。在此重置中，我们通过使用高反应性和选择性试剂开发了新的碳测定反应。 （1）关于添加聚合金属锂有机液簇簇在C-Cerultipe键中添加的实验和理论结果。这项研究首先提供了carfbocupration和1,4个辅助反应的详细机制，并揭示了试剂的簇结构的重要性。（2）高度对启示性将有机金属试剂添加到C = N双键中是通过使用光学活性烯丙基锌试剂在对启示式载体反应的启示式反应过程中开发出的光学活跃的锌试剂，从而实现了（实现）双重键。在烯烃碳测定反应的研究过程中，环丙酮乙酸已发现。碳测定产物，环丙基金属被各种电力捕获。这是将金属在烯烃中添加到烯烃和中间有机金属物种的利用率的第一个例子。

项目成果

E.Nakamura: "Carbometalation of Cyclopropene. Diastereoselective cis-Addition of Zincated Amides, Esters and Hydrazones" J.Org.Chem.62. 792-793 (1997)

E.Nakamura：“环丙烯的碳金属化。锌化酰胺、酯和腙的非对映选择性顺式加成”J.Org.Chem.62。

E.Nakamura: "Carbometalation of Cyclopropene.Diastereoselective cis-Addition of Zincated Amides,Esters and Hydrazones" J.Org.Chem.(印刷中). (1997)

E. Nakamura：“环丙烯的碳金属化。锌化酰胺、酯和腙的非对映选择性顺式加成”J.Org.Chem.（出版中）。

E.Nakamura: "Theoretical Studies on the Addition of Polymetallic Lithium Organocuprate Clusters to Acetylene." J.Am.Chem.Soc.119. 4887-4899 (1997)

E.Nakamura：“多金属锂有机铜簇与乙炔加成的理论研究”。

E.Nakamura: "Theoretical Studies on the Addition of Polymetallic Lithium Organocuprate Clusters to Acetylene." J.Am.Chem.Soc.119. 4887-4889 (1997)

E.Nakamura：“多金属锂有机铜簇与乙炔加成的理论研究”。

M.Nakamura: "Allylzincation of Z-Aldimines.Enantioselective Allylzincation of Z-aldimines in the Presence of Anionic Bis-oxazoline." J.Am.Chem.Soc.118. 8489-8490 (1996)

M.Nakamura：“Z-醛亚胺的烯丙基锌化。在阴离子双恶唑啉存在下，Z-醛亚胺的对映选择性烯丙基锌化。”