1989 Fiscal Year Final Research Report Summary
Fundamental Research for Developing Organotin Reagent
| Project/Area Number |
63430005
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| Research Category |
Grant-in-Aid for General Scientific Research (A)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機化学一般
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| Research Institution | Gunma University |
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Principal Investigator |
MIGITA Toshihiko Gunma University, Faculty of Technology, Professor, 工学部, 教授 (40008412)
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| Co-Investigator(Kenkyū-buntansha) |
SANO Hiroshi Gunma University, Faculty of Technology, Assistant, 工学部, 助手 (40162523)
KOSUGI Masanori Gunma University, Faculty of Technology, Associate Professor, 工学部, 助教授 (60008464)
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| Project Period (FY) |
1988 – 1989
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| Keywords | Organotin Compounds / Union of Heteroaryls / exo-cis Disubstituted Norbornane / Cross Coupling / C-C Bond Formation / Transmetalation / Titanium Chloride |
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| Research Abstract |
Research to establish the utility of organotin compounds as synthetic reagents gave the following new findings. (1). Application of Pd(O) catalyzed coupling reaction to heteroaromatics. Thienyl and pyridyl bromide were fond to couple with organotin reagents which can react with bromobenzene in the presence of Pd(PPh_3)_4, but not with those tin compounds which need the catalyst PdCl_2(Po-tol_3)_2 for the coupling with bromobenzene. The coupling of thienyl and pyridyltin compounds with heteroaryl bromides provides good tools for syntheses of heterobiaryls, heteroteraryls, and heteroquateraryls. (2). Coupling reactions of temary systems catalyzed by transition metal complexes. Coupling reactions of organotins and halides involving insertion of third components such as isonitrile and norbornene were found to take place under catalysis of palladium, giving imines and exo,cis-2,3-disubstituted norbomane, respectively. (3). Addition to carbonyls via transmetalation with TiCl_4.2-Stannylcarbonylates were found to react with aldehydes in the presence of equimolar amount of TiCl_4. The reaction giving gamma-lactones after hydrolytic treatment. Stannylamide, 2-(2-stannyl)pyridine and N-stannyl-p- medioxypropiophenone reacted similarly. The reaction proceeds via transmetalation giving titanium compounds stabilized by intramolecular coordination of N or 0 to Ti.
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