| Project/Area Number |
09305059
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| Research Category |
Grant-in-Aid for Scientific Research (A)
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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 | Nagoya University |
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Principal Investigator |
ITOH Kenji NAGOYA UNIVERSITY, GRADUATE SCHOOL OF ENGINEERING, PROFESSOR, 大学院・工学研究科, 教授 (60023149)
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| Co-Investigator(Kenkyū-buntansha) |
YAMAMOTO Yoshihiko NAGOYA UNIVERSITY, GRADUATE SCHOOL OF ENGINEERING, ASSISTANT PROFESSOR, 大学院・工学研究科, 助手 (60283412)
MATSUDA Isamu NAGOYA UNIVERSITY, GRADUATE SCHOOL OF ENGINEERING, ASSOCIATE PROFESSOR, 大学院・工学研究科, 助教授 (80023266)
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| Project Period (FY) |
1997 – 1999
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| Project Status |
Completed (Fiscal Year 1999)
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| Budget Amount *help |
¥31,700,000 (Direct Cost: ¥31,700,000)
Fiscal Year 1999: ¥6,100,000 (Direct Cost: ¥6,100,000)
Fiscal Year 1998: ¥6,200,000 (Direct Cost: ¥6,200,000)
Fiscal Year 1997: ¥19,400,000 (Direct Cost: ¥19,400,000)
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| Keywords | Transition metal complex catalysts / Catalytic carbon bond formation / Carbocycle synthesis / Ruthenium complex catalysts / Rhodium complex catalysts / Palladium complex catalysts / Organotitanium reagents / Carbonylation / 三成分連結触媒プロセス / ドミノ付加環化 / ラジカル環化 / 1,6-ヘプタジイン / 炭素-炭素結合生成 / 環化反応 / 高次付加環化 / カルボニル環化 / メテニウム錯体 / ロジウム錯体 / ヒドロシリル化 / メチレンラクタム / 有機チタン(III)錯体 / カルボニル / 触媒的付加環化 / 還元カップリング / シリルホルミル化 |
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| Research Abstract |
1. The aim of this research project is to develop novel transition metal mediated reactions to construct complex molecular structures. The following research results were obtained in active research conducted from 1997 to 2000 fiscal years.
2. (1) Highly selective cross-coupling between 1,6-diynes and linear or cyclic alkenes involving heteroatoms or terminal alkynes in the presence of organoruthenium catalysts by way of metallacyclopentadiene intermediates. Unprecedented new domino couplings of dynes with bicyclic alkenes. (2) Based on the mechanistic aspects of rhodium-catalyzed silylformylation of an alkynes, the construction of cyclopentenones, as well as, four-component coupling of an alkynes, a hydrosilane, carbon monoxide, and pyrrolidine was found. (3) Rhodium-carbonyl catalyzed silylative carbocyclization of 1,6-enynes. (4) Rhodium-catalyzed hydrosilylation of 1,6-diynes and its extension to new catalytic annelation to CィイD260ィエD2 fullerene. (5) Rhodium-catalyzed construction of heterocycles from propargyl alcohols and amines. (6) Iridium-catalyzed Michael and aldol reaction of silylenol ethers. (7) Palladium(0)-catalyzed cyclization between electron-deficient alkynes and diynes and its extension to new triyne cyclization. (8) Novel keto-nitrile coupling and pinacol coupling of dials by means of paramagnetic organization reagents. (9) New cyclooctatetraene synthesis starting from a zircona- and titannametalacyclopentadienes.
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