Catalytic Domino Three‐Component Synthesis of Functionalized Heterocycles from Carbon Dioxide

• Published in: ChemSusChem Vol. 17; no. 6; pp. e202301626 - n/a
• Main Authors: Shi, Wangyu, Qiao, Chang, Benet‐Buchholz, Jordi, Kleij, Arjan W.
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 22.03.2024
• Subjects: Alcohols; Carbon dioxide; Carbonates; Chemical synthesis; cyclic carbonates; domino process; Functional groups; homogeneous catalysis; Lewis acid; Michael reaction; ring-expansion process; carbon dioxide; homogeneous catalysis; cyclic carbonates; ring-expansion process; domino process
• ISSN: 1864-5631; 1864-564X
• DOI: 10.1002/cssc.202301626

A catalytic domino, three‐component reaction has been developed for the transformation of carbon dioxide into functionalized six‐membered cyclic carbonates. The catalytic process combines an initial carboxylative cyclization of β‐epoxy alcohols followed by an oxa‐Michael reaction affording an unparalleled scope of heterocyclic structures. The wide range of functional groups, including free‐alcohols, empowers the access to a range of products including C11‐oxo‐based bicyclic heterocycles. The versatility of these functionalized carbonates is further complemented by a series of synthetic diversifications. Control experiments are consistent with the first step of this domino process being promoted by a binary Lewis acid/base catalyst, while the second stage only requires catalytic base. A catalytic domino process has been developed for larger‐ring, functionalized cyclic carbonates with various types of functional groups and involves the intermediacy of a free‐alcohol based six‐membered cyclic carbonate. The domino protocol is propelled by a combination of an Al(III) complex and N‐methyl‐morpholine as supported by various control experiments.