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Integration of CO2 Reduction with Subsequent Carbonylation: Towards Extending Chemical Utilization of CO2
ChemSusChem ( IF 8.4 ) Pub Date : 2018-06-19 , DOI: 10.1002/cssc.201800902
Xian‐Dong Lang 1 , Liang‐Nian He 1, 2
Affiliation  

Currently, it still remains a challenge to amplify the spectrum of chemical fixation of CO2, although enormous progress has been achieved in this field. In view of the widespread applications of CO in a myriad of industrial carbonylation processes, an alternative strategy is proposed in which CO2 reduction to CO is combined with carbonylation with CO generated ex situ, which affords efficiently pharmaceutically and agrochemically attractive molecules. As such, CO2 in this study was efficiently reduced by triphenysilane using CsF to CO in a sealed two‐chamber reactor. Subsequently, palladium‐catalyzed aminocarbonylation, carbonylative Sonogashira coupling of aryl iodides, and rhodium(I)‐mediated Pauson–Khand‐type reaction proceeded smoothly to yield amides, alkynones, and bicyclic cyclopentenones, respectively. Furthermore, the formed alkynones can further be successfully converted to a series of heterocycles, for example, pyrazoles, 3a‐hydroxyisoxazolo[3,2‐a]isoindol‐8‐(3aH)‐one derivatives and pyrimidines in moderate yields. The striking features of this protocol include operational simplicity, high efficiency, and relatively broad application scope, which represents an alternative avenue for CO2 transformation.

中文翻译:

整合CO2还原和后续羰基化:旨在扩展CO2的化学利用

目前,尽管在该领域已经取得了巨大的进步,但是扩大CO 2的化学固定范围仍然是一个挑战。鉴于CO在无数工业羰基化方法中的广泛应用,提出了另一种策略,其中将CO 2还原为CO与羰基化与非原位生成的CO结合,从而有效地提供了药学和农业化学上有吸引力的分子。因此,CO 2在这项研究中,三氯硅烷在封闭的两室反应器中使用CsF到CO有效地还原了CO。随后,钯催化的氨基羰基化,芳基碘化物的羰基化Sonogashira偶联以及铑(I)介导的Pauson–Khand型反应顺利进行,分别产生了酰胺,炔酮和双环环戊烯酮。此外,形成的炔酮可进一步成功转化为一系列杂环,例如吡唑,3a-羟基异恶唑并[3,2 - a ]异吲哚-8-(3a H)-one衍生物和嘧啶类化合物。该协议的显着特征包括操作简便,效率高和相对广泛的应用范围,这代表了CO 2转化的替代途径。
更新日期:2018-06-19
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