Modular Synthesis of ortho‐Thiolated Aryl Esters Enabled with Thiocarbonate through Catellani Strategy

Abstract

Herein, we report a palladium/norbornene/copper co-catalyzed single-step approach that merges selective ortho CÀ H bond esterification with ipso thiolation for construction of synthetically versatile 2-arylthio aryl esters under exceptionally mild conditions. Importantly, this process proceeded in a highly efficient manner, allowing alkoxycarbonyl and thio groups to be installed into one aryl iodides simultaneously by harnessing thiocarbonate as bifunctional reagent. The method has been demonstrated to accommodate good functionalities and features broad substrate scope.

Palladium/norbornene/copper-catalysed intermolecular thio-esterification from ketones: modular access towards tetrasubstituted vinyl sulfides

“…In recent years, reports by Gu, Dai and other researchers on the installation of thiophenol into aromatics through a Catellani reaction have attracted widespread attention, but the synthesis of vinyl sulfides remains challenging. 18 Given the biological importance of tetrasubstituted vinyl sulfides, and in continuation of our long-term research interest in the Pd/NBE chemistry, herein, we describe a complementary and modular α-alkoxycarbonylation/ ipso -thiolation reaction from readily available ketones with thiocarbonate using palladium/norbornene/copper (Pd/NBE/Cu) cooperative catalysis (Scheme 1c). It was envisaged that, through forming enol triflate intermediates, ketones can be converted to a variety of tetrasubstituted vinyl sulfides in a single step.…”

Direct Synthesis of C4-Acyl Indoles via C–H Acylation

“…Therefore, one of the main challenges is delicately regulating the reaction activity between the acylation reagent and the amine to avoid undesired side reactions, in order to attain selective C–H acylation in the synthesis of C4-acyl indoles (Scheme e). In the past few years, further research by the Gu , and Sun ,, groups on C–H acylation reagents has provided us with new ideas to address this challenging problem (Scheme c).…”