Cobalt carbonyl catalyzed reactions of esters and lactones with hydrosilane and carbon monoxide. A novel synthetic method for the introduction of the siloxymethylidene group
The catalytic reactions of esters and lactones with hydrosilane and carbon monoxide in the presence of Co/sub 2/(CO)/sub 8/ have been studied in detail with the emphasis being focused on their utility in organic synthesis. The catalytic reaction of secondary alkyl acetates underwent clean incorporation of carbon monoxide to give (siloxymethylidene)alkanes (enol silyl ethers). Lactones of secondary alkyl ester type reacted similarly. The siloxymethylidenation products were converted to aldehydes. Primary alkyl acetates gave several products in a nonselective manner. In the case of tertiary alkyl esters, no incorporation of carbon monoxide took place except for bridgehead alkyl acetates. The mechanism of the catalytic reaction has been proposed, and the importance of the silycobalt carbonyl, R/sub 3/SiCO(CO)/sub 4/, as the key catalyst species has been suggested. The high affinity of the silicon in R/sub 3/SiCo(CO)/sub 4/ toward the oxygen atom in the ester is suggested to be the driving force for the formation of alkylcobalt carbonyls as the intermediates. This step illustrates a new methodology for the formation of a carbon-transition metal bond.
- Research Organization:
- Osaka Univ., Japan
- OSTI ID:
- 7222763
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:23; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CATALYSIS
CATALYSTS
CATALYTIC EFFECTS
CHALCOGENIDES
CHEMICAL BONDS
CHEMICAL REACTIONS
COBALT COMPOUNDS
DATA
ESTERS
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
HYDRIDES
HYDROGEN COMPOUNDS
INFORMATION
LACTONES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SILICON COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
SILANES
SILICON COMPOUNDS
TRANSITION ELEMENT COMPOUNDS