Mechanistic insights into the Cu( ii )/DBU-catalyzed incorporation of CO 2 into homopropargylic amines

• Published in: New journal of chemistry 2023-03, Vol.47 (12), p.5691-5700
• Main Authors: Yuan, Binfang, Liu, Senmao, Liu, Tian, Li, Qing, Wang, Yulu, Guo, Zhihui, Guo, Xiaogang, Huang, Huisheng, He, Rongxing
• Format: Article
• Language: English
• ISSN: 1144-0546; 1369-9261
• DOI: 10.1039/D2NJ05809J

The mechanisms of Cu( ii )/DBU-catalyzed carboxylation of homopropargylic amines with CO 2 to construct 6-methylene-1,3-oxazin-2-ones are studied via density functional theory. The calculations suggest that Cu( ii ) catalysts exhibit a positive effect on the process of intramolecular cyclization, and the catalytic activities of which are determined by their coordination abilities ((DBU)CuCl 2 < CuCl 2 < [(DBU)CuCl] + ). Furthermore, three roles of DBU are revealed in this study: (a) DBU acts as the proton-acceptor to capture a proton of homopropargylic amines. (b) DBU attacks CO 2 to form DBU-CO 2 as the nucleophilic agent, and then DBU-CO 2 assists the H + shift as the proton shuttle. (c) DBU serves as the ligand replacing one Cl − anion of CuCl 2 , forming the activated species [(DBU)CuCl] + . Besides, the theoretical study well explains the selectivity of Cu( ii )-catalyzed reactions (6- vs. 7-membered cyclization), and the 6-membered products are found to be formed selectively. Overall, our work reproduces the experimental results well and provides an indispensable understanding of CO 2 -conversion to synthesize various high-value chemicals with the assistance of a catalytic system combining transition-metal catalysts and organic bases.