| Project/Area Number |
18350052
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Synthetic chemistry
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| Research Institution | Osaka University |
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Principal Investigator |
KAMBE Nobuaki Osaka University, Graduate School of Engineering, Professor (60144432)
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| Co-Investigator(Kenkyū-buntansha) |
TERAO Jun Kyoto University, Graduate School of Engineering, Associate Professor (00322173)
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| Project Period (FY) |
2006 – 2007
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| Project Status |
Completed (Fiscal Year 2007)
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| Budget Amount *help |
¥17,390,000 (Direct Cost: ¥15,200,000、Indirect Cost: ¥2,190,000)
Fiscal Year 2007: ¥9,490,000 (Direct Cost: ¥7,300,000、Indirect Cost: ¥2,190,000)
Fiscal Year 2006: ¥7,900,000 (Direct Cost: ¥7,900,000)
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| Keywords | Cu-catalyst / Ni-catalyst / eneynes / vinyl Grignard reagents / dimerization / chlorosilanes / cyclic ethers / alkyl halides / ハロゲン化アルキル / グリニャール試薬 / クロスカップリング反応 / アニオン性錯体 / ブタジエン / 有機アルミニウム試薬 / シリル化反応 |
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| Research Abstract |
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.
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