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Ligand-Controlled Regiodivergent Thiocarbonylation of Alkynes toward Linear and Branched α,β-Unsaturated Thioesters
Han-Jun Ai1, Wangyang Lu2, Xiao-Feng Wu1,3
1Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Straße 29a, 18059, Rostock, Germany.
Abstract:
Thiocarbonylation of alkynes offers an ideal procedure for the synthesis of unsaturated thioesters. A robust ligand-controlled regioselective thiocarbonylation of alkynes is developed. Utilizing boronic acid and 5-chlorosalicylic acid as the acid additive to in situ form 5-chloroborosalicylic acid (5-Cl-BSA), and bis(2-diphenylphosphinophenyl)ether (DPEphos) as the ligand, linear α,β-unsaturated thioesters were produced in a straightforward manner. Switching the ligand to tri(2-furyl)phosphine can turn the reaction selectivity to give branched products. Remarkably, this approach also represents the first example on thiocarbonylation of internal alkynes.
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