Endogenous X–CO species enable catalyst-free formylation prerequisite for CO<sub>2</sub> reductive upgrading
作者:Hongguo Wu、Wenshuai Dai、Shunmugavel Saravanamurugan、Hu Li、Song Yang
DOI:10.1039/d0gc02142c
日期:——
(>90%) from catalyst-free reductive upgrading of CO2 under mild conditions (50 °C). The endogenous X–CO species, derived from the N-methyl-substituted amide-based solvent [Me2N–C(O)–R], especially PolarClean, and O-formyl group [O–C(O)–H] of in situ formed silyl formate, were found to play a prominent promotional role in the activation of the used hydrosilane for reductive CO2 insertion, as demonstrated
CO 2是温室气体的主要成分,目前已被开发为一种有前途的碳原料替代品。在各种转化途径中,经历催化还原的CO 2可以提供氢/能量载体和增值化学品,而特定的含金属催化剂或有机催化剂通常是顺利进行所涉及的反应过程的先决条件。在这项工作中,可以在温和的条件下通过无催化剂的CO 2还原提质,以高收率(> 90%)合成甲酸和含N的苯并杂环化合物(包括各种苯并咪唑,苯并噻唑和苯并恶唑)以及硅烷醇。50°C)。来自N的内源X–C O物种甲基取代的酰胺基溶剂[Me 2 N–C(O)–R],尤其是PolarClean,以及原位形成的甲硅烷基甲酸酯的O-甲酰基[ OC – O (H)–H]如密度泛函理论(DFT)计算和同位素标记实验所证明的那样,在用于还原的CO 2插入的已用氢硅烷的活化中,显着的促进作用。此外,还描述了反应机理和基于条件的敏感性评估。