Development of New Processes for the Carbon Monoxide in Chemical Industries

该项目的目的是通过使用一氧化碳作为羰基化试剂来开发新的羰基化工艺。本项目的研究重点是在合成化学和化学工业中的许多有用的羰基化反应中，由典型元素，特别是重杂原子化合物而不是过渡金属作为催化剂起重要作用的过程。本项目包括以下三个主题，并带来了一些重要的结果，这些结果将开辟一氧化碳羰基化反应的新领域。1.第一个主题“硒的羰基化”导致了在羰基化合物的α-碳上的新的硒羧化反应的发展，例如酮，醛和酰胺。该反应在室温或更低温度下在一氧化碳的大气压下进行，在用烷基卤化物捕获硒代羧酸锂后得到硒代羧酸烷基酯，所述硒代羧酸锂是通过在羰基化合物的α-碳上引入SeCO单元而原位形成的。2.在钯催化剂的作用下，通过在炔中同时引入一氧化碳和杂原子，在碳-碳三键的碳原子上区域选择性地引入硒代和硒代羰基，以高产率合成了丙烯酸硒苯酯。同时建立了一种简便的苯硒代羰基选择性还原为甲酰基的方法，从而将这两个反应结合起来，实现了硒代羰基化反应。3.有机卤化物与一氧化碳的非常有效的“自由基羰基化”反应也通过使用锡烷或硅烷在AIBN作为自由基引发剂的存在下实现。该反应是一种非常独特的方法，将成为卤化烃羰基化合成醛、酮的一种有用的方法。

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.