The development of versatile catalyst systems and new transformations for the utilization of carbon dioxide (CO₂) is of great interest and significance. This Personal Account reviews our studies on the exploration of the reactions of CO₂ with various substrates by the use of N‐heterocyclic carbene (NHC)‐copper catalysts. The carboxylation of organoboron compounds gave access to a wide range of carboxylic acids with excellent functional group tolerance. The C−H bond carboxylation with CO₂ emerged as a straightforward protocol for the preparation of a series of aromatic carboxylic esters and butenoates from simple substrates. The hydrosilylation of CO₂ with hydrosilanes provided an efficient method for the synthesis of silyl formate on gram scale. The hydrogenative or alkylative carboxylation of alkynes, ynamides and allenamides yielded useful α,β‐unsaturated carboxylic acids and α,β‐dehydro amino acid esters. The boracarboxylation of alkynes or aldehydes afforded the novel lithium cyclic boralactone or boracarbonate products, respectively. The NHC‐copper catalysts generally featured excellent functional group compatibility, broad substrate scope, high efficiency, and high regio‐ and stereoselectivity. The unique electronic and steric properties of the NHC‐copper units also enabled the isolation and structural characterization of some key intermediates for better understanding of the catalytic reaction mechanisms.

中文翻译：

---

N-杂环碳-铜催化剂与二氧化碳的羧化反应

通用催化剂系统的开发和利用二氧化碳（CO ₂）的新转化具有极大的兴趣和意义。本个人帐户回顾了我们对使用N杂环卡宾（NHC）铜催化剂探索CO ₂与各种底物反应的研究。有机硼化合物的羧化使人们能够获得具有优异官能团耐受性的各种羧酸。用CO _2进行的C H键羧化反应是从简单底物制备一系列芳族羧酸酯和丁烯酸酯的直接方法。CO ₂的氢化硅烷化用氢化硅烷的合成提供了一种有效的方法，用于合成克级的甲酸甲硅烷基酯。炔烃，炔基酰胺和烯丙基酰胺的氢化或烷基化羧化反应会产生有用的α，β-不饱和羧酸和α，β-脱氢氨基酸酯。炔烃或醛的硼碳酸酯化分别提供了新型的环状环状硼内酯或硼碳酸盐产品。NHC-铜催化剂通常具有出色的官能团相容性，广泛的底物范围，高效率以及高的区域和立体选择性。NHC铜单元的独特电子和位阻特性也使某些关键中间体的分离和结构表征能够更好地理解催化反应机理。