Metal-Free, Adjustable, and Recyclable Catalytic Systems for the Construction of C–C Bonds by Activating Propargylic Alcohols

• Published in: Journal of organic chemistry 2022-09, Vol.87 (17), p.11669-11680
• Main Authors: Wang, Ning, Li, Zengmin, Hou, Qin, Han, Feng, Yan, Yucai, Zhang, Jian, Miao, Chengxia
• Format: Article
• Language: English
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/acs.joc.2c01305

Pyrano­[3,2-c]­coumarin derivatives and C3-substituted 4-hydroxycoumarins as important skeletal structures of active natural products and pharmaceutically relevant molecules have received increasing attention. However, developing an adjustable system for selectively synthesizing them is still a challenging task. Herein, sulfonic acid-functionalized ionic liquid was successfully used as the catalyst for the alkylation of 4-hydroxycoumarin derivatives with secondary aromatic propargylic alcohols using dimethyl carbonate as the green solvent, giving up to 98% yield. On the other hand, protonated imidazole-based ionic liquid-catalyzed cyclization was also selectively achieved with a nearly quantitative yield. Developed metal-free catalytic systems exhibited well adjustable and recyclable properties, avoiding the contamination of metal and halogen, reducing the neutralization after the reaction, and benefiting the separation between the catalyst and the product. New strategies were applied for performing the gram-scale reaction smoothly. The adjustable systems might occur through two different mechanisms involving propargylic or allenic carbocation and hydrogen bonding effects between the catalysts and the substrates.