Unusual DBU-catalyzed decarboxylative formation of allylic thioethers from vinyl cyclic carbonates and thiols. Issue 24 (27th October 2022)

• Record Type: Journal Article
• Authors: Ni, Jixiang; Lanzi, Matteo; Kleij, Arjan W.
• Is Part Of: Organic chemistry frontiers. Volume 9:Issue 24(2022)
• Page Start: 6780
• Page End: 6785
• Publication Date: 2022-10-27
• Subjects: Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1039/d2qo01511k
• Languages: English
• ISSNs: 2052-4110

Abstract

Abstract : Vinyl cyclic carbonates undergo an exo -cyclic attack by thiol nucleophiles under DBU catalysis to form allylic thioether products in moderate to good yields through a decarboxylative process under attractive process conditions. Abstract : An unanticipated exo -cyclic nucleophilic attack of thiol reagents on vinyl cyclic carbonates is described under DBU catalysis. The process allows the production of allylic thioethers under moderately mild conditions following a sequence of steps that involve a nucleophilic attack of the thiol on the C-terminus of the CC bond, carbonate ring-opening, and decarboxylation followed by final protonation. This unusual thiol-induced ring-opening complements the previously reported and more widely observed endo -cyclic nucleophilic attack on either the carbonate or methylene carbon centers, and therefore amplifies the reactivity modes that can be accessed with these heterocycles.