Development of New Processes for the Carbon Monoxide in Chemical Industries

该项目的目的是利用一氧化碳作为羰基化试剂开发新的羰基化工艺。研究兴趣集中在典型元素，特别是重杂原子化合物所促进的过程，而不是过渡金属，它们在合成化学和化学工业中许多有用的羰基化反应中起着重要的催化剂作用。该项目包括以下三个主要主题，并带来了一些重要的结果，这些结果将开辟与一氧化碳羰基化反应的新领域。1. 第一个主题“硒的羰基化”导致了羰基化合物（如酮、醛和酰胺）α碳上新的硒羧化反应的发展。该反应在室温或更低的一氧化碳大气压下进行，通过在羰基化合物的α碳上引入SeCO单元，在捕获硒代羧化锂后，得到硒代烷基硒代羧化锂和烷基卤化物。2. “一氧化碳和杂原子部分的同时引入”是通过使用钯催化剂实现的，其中苯硒基和苯硒羰基在碳-碳三键的碳上选择性地引入，得到产率高的硒苯基丙烯酸酯。建立了一种方便的选择性还原苯基硒羰基为甲酰基的方法，从而将这两个反应结合起来，实现了硒酰基化反应。3. 在AIBN作为自由基引发剂的情况下，使用锡烷或硅烷也可以实现有机卤化物与一氧化碳的“自由基羰基化”反应。该反应是一种独特的反应，是烷基卤化物羰基化生成醛和酮的有效方法。

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.