权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

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.

镍催化偶联反应：发现其（π-烯丙基）镍钯配合物在温和条件下催化烷基卤化物与烷基格里格拉德试剂的交叉偶联反应。通过在ni催化体系中使用具有两个图二烯单元的配体，可以显著加速交叉偶联反应，并且可以用二烷基锌试剂代替格氏试剂作为偶联剂。还发现二氯化镍与乙烯基格氏试剂反应生成含丁二烯和乙烯基的镍配合物，并与环醚反应生成烷基化均烯丙基格氏试剂，收率较高。铜催化的偶联反应：在炔配体存在下，铜催化烷基氯化物的交叉偶联反应。然而，在类似的条件下，仲烷基和叔烷基格氏试剂与二烯或炔通过碳磁反应得到烷基化烯丙基镁化合物。用各种亲电试剂如烷基溴、氯硅烷、烯酮、酸卤化物或二氧化碳捕获这样形成的化合物，根据亲电试剂的结构提供相应的烯烃或烯。钛催化反应：发现了二茂钛配合物催化苯乙烯与烷基卤化物和烷基格氏试剂的烷基化反应。二氯化二茂钛与乙烯基Grignrad试剂反应形成二茂钛-二烯配合物，该配合物随后与另一乙烯基卤化镁反应形成盐配合物。在烷基卤化物存在的情况下，通过在丁二烯单元上加成烷基自由基，然后进行金属转化，形成烷基化烯丙基Grignrad试剂。