Development of New Processes for the Carbon Monoxide in Chemical Industries

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The aim of this project was to develop new carbonylation processes by the use of carbon monoxide as a carbonylation reagent. The research interest was focused on the processes promoted by typical elements, especially heavy heteroatom compounds, rather than transition metals which play important roles as catalysts in a number of useful carbonylation reactions not only in synthetic chemistry but also in chemical industries This project comprised three major themes mentioned below and brought several important results which will open up new fields of carbonylation reactions with carbon monoxide. 1. The first theme "Carbonylation by Selenium" led to a development of a new selenocarboxylation reaction at the alpha-carbon of carbonyl compounds, such as ketones, aldehydes, and amides. This reaction proceeds under atmospheric pressure of carbon monoxide at room temperature or below to give Se-alkyl selenocarboxylates after trapping of lithium selenocarboxylates, which are formed in situ via introduction of a SeCO unit at an alpha-carbon of carbonyl compounds, with alkyl halides. 2. The "Concomitant Introduction of Carbon Monoxide and Heteroatom Moieties" into alkynes was achieves by the use of a palladium catalyst, where phenylseleno and phenylselenocarbonyl groups are introduced regioselectively at the carbons of carbon-carbon triple bonds to give Se-phenyl acrylates in good yields. A convenient method for the selective reduction of phenylselenocarbonyl group to formyl group was also established, and so the combination of these two reactions led to the achievement of selenoformylation reaction. 3. Very efficient "Radical Carbonylation" reactions of organo halides with carbon monoxide were achieved also by the use of stannanes or silanes in the presence of AIBN as a radical initiator. This reaction is very unique nad will be a useful method for the carbonylation of alkyl halides to give aldehydes and ketones.