Development of Synthetic Reactions Catalyzed by Transition Metal Complexes Having π-Electron Accepting Carbon Ligands

具有π电子接受碳配体的过渡金属配合物催化的合成反应研究进展

基本信息

批准号：
18350052
负责人：
KAMBE Nobuaki
金额：
$ 11.13万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2006
资助国家：
日本
起止时间：
2006 至 2007
项目状态：
已结题

项目摘要

Ni-catalyzed coupling reactions:It has been revealed that bis (π-allyl) nickel and palladium complexes catalyze cross-coupling reaction between alkyl halides and alkyl Grignrad reagents under mild conditions. By the use of ligands that have two tutadiene units in the molecule in Ni-catalyzed systems, cross-coupling reaction was found to be dramatically accelerated and dialkyl zinc reagents can be used as the coupling partners instead of Grignard reagents. It was also found that nickel dichloride reacts with vinyl Grignard reagents to form nicklate comples possessing butadiene and vinyl group which reacted with cyclic ethers to give alkylated homoallyl Grignard reagents in good yields.Cu-catalyzed coupling reactions: Cu catalyzes cross coupling reaction of alkyl chlorides in the presence of alkyne ligands. Under similar conditions, however, secondary and tertiary alkyl Grignard reagents reacted with dienes or enynes to give alkylated allylmagnesium compounds via carbomagnesation. Trapping of thus formed compounds with various electrophiles such as alkyl bromides, chlorosilanes, enones, acid halides, or carbon dioxides, afforded corresponding olefins or allenes depending on the structures of electrophiles. Ti-catalyzed reaction: titanocene complex was found to catalyze alkylation of styrenes with alkyl halides and alkyl Grignard reagents. Titanocene dichloride reacted with vinyl Grignrad reagents to form a titanocene-diene complex which then react with another vinylmagnesium halides to form an ate complex. In the presence of alkyl halides, alkylated allyl Grignrad reagents were formed via addition of alkyl radical to the butadiene units followed by transmetallation.

Ni催化的耦合反应：已经表明，在轻度条件下，BIS（π-酰基）镍和钯络合物催化了酸卤化物和醇酸卤化物和酸性Grignrad试剂之间的交叉偶联反应。通过在Ni催化系统中的分子中使用两个曲二烯单元的配体，发现交叉偶联反应是动态加速的，并且可以将二烷基锌试剂用作耦合伙伴代替Grignard Reagents。 It was also found that nickel dichloride reacts with vinyl Grignard reagents to form nicklate completes possesses butadiene and vinyl group which reacted with cyclic ethers to give alkylated homoallyl Grignard reagents in good yields.Cu-catalyzed coupling reactions: Cu catalyzes cross coupling reaction of alkyl chlorides in the presence of alkyne ligands.然而，在类似条件下，二级和第三级烷基grignard试剂与二烯或烯烯反应，通过碳镁化来产生烷基化的烯丙基烯丙基化合物。根据电力的结构，捕获了与各种电物质（如烷基溴化物，氯硅烷，烯酮，酸卤化物或二氧化碳）的形成化合物，可根据电力的结构提供相应的烯烃或艾伦。 Ti催化反应：发现钛二晶复合物可催化烷基卤化物和烷基尖齿试剂的苯乙烯。钛二氯化与乙烯基Grignrad试剂反应，形成钛二烯型二烯络合物，然后与另一个乙烯基烟碱卤化物反应，形成一个ate络合物。在存在烷基卤化物的情况下，烷基化的烯丙基灰grignrad试剂是通过在丁二烯单元中添加烷基自由基，然后进行跨金属形成的。