| Project/Area Number |
14350477
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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 Nobuyuki Osaka University, Graduate School of Engineering, Professor, 大学院・工学研究科, 教授 (60144432)
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| Co-Investigator(Kenkyū-buntansha) |
TERAO Jun Osaka University, Graduate School of Engineering; Lecturer, Assistant Professor, 大学院・工学研究科, 助手 (00322173)
KUNIYASU Hitoshi Osaka University, Graduate School of Engineering, Lecturer, 大学院・工学研究科, 講師 (00252594)
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| Project Period (FY) |
2002 – 2003
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| Project Status |
Completed (Fiscal Year 2003)
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| Budget Amount *help |
¥16,200,000 (Direct Cost: ¥16,200,000)
Fiscal Year 2003: ¥5,700,000 (Direct Cost: ¥5,700,000)
Fiscal Year 2002: ¥10,500,000 (Direct Cost: ¥10,500,000)
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| Keywords | cross-coupling reaction / Grignard reagents / alkyl halides / alkyl fluorides / palladium catalyst / nickel catalyst / chlorosilane / butadiene / Ni錯体 / グリニャール試薬 / アート錯体 |
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| Research Abstract |
A novel method for cross-coupling reaction of Grignard reagents with alkyl chlorides, bromides, and tosylates has been developed with the aid of Ni catalysts. This reaction proceeds efficiently by the use of primary and secondary alkyl-or arylmagnesium halides under mild conditions. The use of 1,3-butadiene as an additive instead of phosphine ligands is the key to attain high yields of the cross-coupling products. We also revealed the first example of metal-catalyzed cross-coupling reaction of alkyl fluorides with Grignard reagents. These reactions proceed efficiently between primary alkyl fluorides and various Grignard reagents under mild conditions in the presence of nickel or copper salts. Anew method for a highly regioselective four-component coupling reaction of 2 molecules of dienes, a chlorosilane and a Grignard reagent has been developed with the aid of nickel catalysts. This reaction provides 1,6-dienes having an allylsilane unit. This study provides the first example of C-Si bond-forming reaction using chlorosilanes catalyzed by late transition metals. On the other hand, we have also developed a new method for Pd-catalyzed regioselective two C-Si bonds and one C-C bond forming reaction using chlorosilane. This reaction proceeds stereoselectively by the use of aryl or allyl substituted chlorosilanes giving rise to 1, 6-octadienes having two allylsilane unit.
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