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Cooperative redox activation for carbon dioxide conversion

机译:协同氧化还原活化法转化二氧化碳

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摘要

A longstanding challenge in production chemistry is the development of catalytic methods for the transformation of carbon dioxide into useful chemicals. Silane and borane promoted reductions can be fined-tuned to provide a number of C1-building blocks under mild conditions, but these approaches are limited because of the production of stoichiometric waste compounds. Here we report on the conversion of CO2 with diaryldisilanes, which through cooperative redox activation generate carbon monoxide and a diaryldisiloxane that actively participate in a palladium-catalysed carbonylative Hiyama-Denmark coupling for the synthesis of an array of pharmaceutically relevant diarylketones. Thus the disilane reagent not only serves as the oxygen abstracting agent from CO2, but the silicon-containing ‘waste', produced through oxygen insertion into the Si–Si bond, participates as a reagent for the transmetalation step in the carbonylative coupling. Hence this concept of cooperative redox activation opens up for new avenues in the conversion of CO2.
机译:生产化学领域的长期挑战是开发催化方法,将二氧化碳转化为有用的化学物质。可以对硅烷和硼烷促进的还原进行微调,以在温和的条件下提供许多C1结构单元,但是由于化学计量废化合物的产生,这些方法受到限制。在这里,我们报告了二芳基二硅烷对CO2的转化,通过协同氧化还原活化反应生成一氧化碳和二芳基二硅氧烷,它们积极参与钯催化的羰基化Hiyama-Denmark偶联反应,以合成一系列药学上相关的二芳基酮。因此,乙硅烷试剂不仅充当二氧化碳中的氧气提取剂,而且通过将氧气插入Si-Si键中而产生的含硅“废物”也参与了羰基化偶联过程中的过渡金属化试剂。因此,这种协同氧化还原活化的概念为CO 2转化开辟了新途径。

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