1992 Fiscal Year Final Research Report Summary
Development of new methods for the carbon-carbon bond formation catalyzed by transition-metal complexes
| Project/Area Number |
03650671
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機工業化学
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| Research Institution | Nagoya University |
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Principal Investigator |
MATSUDA Isamu Nagoya University, Engineering, Assistant Professor, 工学部, 講師 (80023266)
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| Project Period (FY) |
1991 – 1992
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| Keywords | Rhodium complex / Aldol type coupling / Silylformylation / Silylcarbonylation / Incorporation of CO / alpha-Silylmethylene-beta-lactam / 2-Silylmethyl-2-alkenal |
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| Research Abstract |
The author found that combination of rhodium complex and triorganosilane is useful for a specific carbon-carbon bond formation. In order to search a novel synthetic method, the following subjects were focussed in the first year,(i)three component coupling composed of alpha,beta-unsaturated carbonyl compound, aldehyde, and trialkylsilane, which is catalyzed by Rh_4(CO)_<12> under neutral conditions,(ii)mechanistic approach to silylformylation of acetylenic compounds, and (iii)exploitation of new one-pot method to construct alpha-silylmethylene-beta- lactones or alpha-silylmethylene-beta-lactams from propargylic alcohol or amine derivatives. All these projects were completed successfully. It was revealed that oxidative addition of triorganosilane to rhodium metal plays an important role as the fundamental step in these transformations. Bulky substituents on the propargylic carbon and triorganosilane are advantageous for the formation of lactones or lactams.
The following subjects are the main concern in the second year, (i)regio-defined silylformylation of internal acetylenic compounds and (ii)catalytic formation of 2-silylmethyl-2- alkenals. An intramolecular version of silylformylation is a reliable method for the distiction between two acetylenic carbons. The latter subject was attained successfully by the interaction of two equimolar of triorganosilane with propargylamine or propargylalcohol derivatives.
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