Fujihara Tetsuaki, Tsuji Yasushi
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan.
Beilstein J Org Chem. 2018 Sep 19;14:2435-2460. doi: 10.3762/bjoc.14.221. eCollection 2018.
Carbon dioxide (CO) is one of the most important materials as renewable chemical feedstock. In this review, the Co- and Rh-catalyzed transformation of CO via carbon-carbon bond-forming reactions is summarized. Combinations of metals (cobalt or rhodium), substrates, and reducing agents realize efficient carboxylation reactions using CO. The carboxylation of propargyl acetates and alkenyl triflates using cobalt complexes as well as the cobalt-catalyzed reductive carboxylation of α,β-unsaturated nitriles and carboxyamides in the presence of EtZn proceed. A Co complex has been demonstrated to act as an efficient catalyst in the carboxylation of allylic C(sp)-H bonds. Employing zinc as the reductant, carboxyzincation and the four-component coupling reaction between alkyne, acrylates, CO, and zinc occur efficiently. Rh complexes also catalyze the carboxylation of arylboronic esters, C(sp)-H carboxylation of aromatic compounds, and hydrocarboxylation of styrene derivatives. The Rh-catalyzed [2 + 2 + 2] cycloaddition of diynes and CO proceeds to afford pyrones.
二氧化碳（CO）是最重要的可再生化学原料之一。在本综述中，总结了钴和铑催化的通过碳-碳键形成反应对CO的转化。金属（钴或铑）、底物和还原剂的组合实现了使用CO的高效羧化反应。使用钴配合物对炔丙基乙酸酯和烯基三氟甲磺酸酯进行羧化，以及在EtZn存在下钴催化的α，β-不饱和腈和羧酰胺的还原羧化反应都能进行。已证明一种钴配合物在烯丙基C(sp)-H键的羧化反应中可作为高效催化剂。以锌作为还原剂，羧基锌化以及炔烃、丙烯酸酯、CO和锌之间的四组分偶联反应能有效发生。铑配合物还催化芳基硼酸酯的羧化反应、芳香族化合物的C(sp)-H羧化反应以及苯乙烯衍生物的氢羧化反应。铑催化的二炔与CO的[2 + 2 + 2]环加成反应可生成吡喃酮。
