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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：双（π-烯丙基）镍和钯配合物在温和条件下催化烷基卤和烷基格氏试剂的交叉偶联反应。在镍催化体系中，通过引入分子中含有两个配体单元的配体，可以显著地加快交叉偶联反应的进行，并且可以用二烷基锌试剂代替格氏试剂作为偶联配体。研究还发现，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酸盐配合物，后者与环醚反应生成烷基化的高烯丙基格氏试剂，产率较高。铜催化偶联反应：在炔配体存在下，铜催化烷基氯的交叉偶联反应。在相似的条件下，仲烷基和叔烷基格氏试剂与二烯或烯炔反应，通过碳镁化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、酰卤或二氧化碳捕获由此形成的化合物，根据亲电试剂的结构得到相应的烯烃或丙二烯。钛催化反应：发现茂钛配合物催化苯乙烯与烷基卤和烷基格氏试剂的烷基化反应。二氯二茂钛与乙烯基格氏试剂反应形成二茂钛-二烯络合物，然后与另一种乙烯基卤化镁反应形成酯络合物。在烷基卤化物存在下，通过将烷基自由基加成到丁二烯单元上，然后进行transmetlate，形成烷基化烯丙基格氏试剂。