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:
- 金额:$ 11.13万
- 依托单位:
- 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
- 来源:
- 关键词:
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。
项目成果
期刊论文数量(0)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Nickel-catalyzed dimerization coupling reactions of vinyl Grignard reagents with 3, 4-membered cyclic ethers and chlorosilanes
镍催化乙烯基格氏试剂与3、4元环醚和氯硅烷的二聚偶联反应
- DOI:
- 发表时间:2007
- 期刊:
- 影响因子:0
- 作者:Yuuki Fujii;Jun Terao;Hitoshi Kuniyasu;Nobuaki Kambe
- 通讯作者:Nobuaki Kambe
チタノセン触媒及びグリニャール試薬存在下、ブロモアルキルェーテルを用いたスチレン類のダブルアルキル化及び脱水素アルキル化反応
在二茂钛催化剂和格氏试剂存在下,使用溴代烷基醚对苯乙烯进行双烷基化和脱氢烷基化
- DOI:
- 发表时间:2006
- 期刊:
- 影响因子:0
- 作者:加藤雄一朗;寺尾 潤;神戸宣明
- 通讯作者:神戸宣明
C-C and C-Si Bond Forming Reactions Catalyzed by Transition Metal Ate Complexes.
过渡金属 Ate 配合物催化的 C-C 和 C-Si 键形成反应。
- DOI:
- 发表时间:2006
- 期刊:
- 影响因子:0
- 作者:寺尾 潤;尾田昭弘;渡部弘康;神戸宣明;灰野岳晴;灰野岳晴;N. Kambe
- 通讯作者:N. Kambe
チタノセン触媒及びグリニャール試薬存在下、ブロモアルキルェーテルを用いたスチレンの位置選択的アルキル化反応
在二茂钛催化剂和格氏试剂存在下,使用溴代烷基醚对苯乙烯进行区域选择性烷基化
- DOI:
- 发表时间:2006
- 期刊:
- 影响因子:0
- 作者:加藤雄一朗;寺尾 潤;神戸宣明
- 通讯作者:神戸宣明
Cross-coupling of Alkyl Halides with Grignard Reagent Using Nickel and Palladium Complexes Bearing η^3-Alll Ligand as Catalysts
使用带有 η^3-All 配体的镍和钯配合物作为催化剂进行烷基卤化物与格氏试剂的交叉偶联
- DOI:
- 发表时间:2007
- 期刊:
- 影响因子:0
- 作者:Jun Terao;Yoshitaka Naitoh;Hitoshi Kuniyasu;Nobuaki Kambe
- 通讯作者:Nobuaki Kambe
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KAMBE Nobuaki其他文献
KAMBE Nobuaki的其他文献
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{{ truncateString('KAMBE Nobuaki', 18)}}的其他基金
Development of Stereoselective Formation of Carbon-Halogen Bonds
碳-卤键立体选择性形成的研究进展
- 批准号:
24655032 - 财政年份:2012
- 资助金额:
$ 11.13万 - 项目类别:
Grant-in-Aid for Challenging Exploratory Research
Development and Control of Highly Efficient Catalytic Systems for Cross-and Multicomponent-Coupling Reactions
交叉和多组分偶联反应高效催化系统的开发和控制
- 批准号:
20225004 - 财政年份:2008
- 资助金额:
$ 11.13万 - 项目类别:
Grant-in-Aid for Scientific Research (S)
Efficient Carbon Skeleton Constructing Reactions by Use of Small Hydrocarbon Compounds or Carbon Monoxide
使用小烃化合物或一氧化碳的高效碳骨架构建反应
- 批准号:
17065015 - 财政年份:2005
- 资助金额:
$ 11.13万 - 项目类别:
Grant-in-Aid for Scientific Research on Priority Areas
Activation of Olefins with Polarity Inversion and Its Synthetic Application
烯烃极性反转活化及其合成应用
- 批准号:
12450355 - 财政年份:2000
- 资助金额:
$ 11.13万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Generation and Reaction of Hyperralent Hetero-atom
高惰性杂原子的产生与反应
- 批准号:
10450335 - 财政年份:1998
- 资助金额:
$ 11.13万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
相似海外基金
Development of Ni catalyst for carbon monoxide hydrogenation based on adsorption ability control
基于吸附能力控制的一氧化碳加氢镍催化剂的研制
- 批准号:
08650919 - 财政年份:1996
- 资助金额:
$ 11.13万 - 项目类别:
Grant-in-Aid for Scientific Research (C)