Pd-Catalyzed Double-Decarbonylative Aryl Sulfide Synthesis through Aryl Exchange between Amides and Thioesters

Abstract

We report the palladium-catalyzed double-decarbonylative synthesis of aryl thioethers by an aryl exchange reaction between amides and thioesters. In this method, amides serve as aryl donors and thioesters are sulfide donors, enabling the synthesis of valuable aryl sulfides. The use of Pd/Xantphos without any additives has been identified as the catalytic system promoting the aryl exchange by C­(O)–N/C­(O)–S cleavages. The method is amenable to a wide variety of amides and sulfides.

An efficient and straightforward approach for accessing thionoesters via palladium-catalyzed C–N cleavage of thioamides

“…Based on the known palladium chemistry, 106–109 a plausible mechanism for the catalytic reaction was proposed (Scheme 7): (i) oxidative addition takes place at the C–N bond of thioamide 1a to give thio-acylpalladium( ii ) complex II ; (ii) following transmetalation, complex III is produced by the reaction of benzyl alcohol 2a ; and (iii) then, reductive elimination occurs to form thionoester product 3a and regenerates the Pd(0) species I .…”

Recent Metal-Catalyzed Methods for Thioether Synthesis

“…Szostak, Liu, and co-workers also developed a Pd-catalyzed double decarbonylative coupling of thioesters with amides. 97 Later on, this methodology was expanded to couple carboxylic acids with thioesters. 98 As another substrate variation, α-oxo thioesters 34 were used by Xu, Wei, and co-workers (Scheme 25 ).…”

Regioselective 1,2-carbosulfenylation of unactivated alkenesviadirected nickel catalysis

“…In addition, organosul des can be readily transformed into the corresponding sulfoxides and sulfones, which often act as versatile building blocks for organic synthesis. [7][8][9] The synthetic approaches for the e cient construction of C-S bonds include Michael addition, S N 2-type alkylation, cross-coupling, [10][11][12][13] and C-H functionalization [14][15][16] . One powerful and more attractive protocol for their construction is through the carbosulfenylation of alkenes, because this leads to the simultaneous introduction of a carbogenic and a thiol group across a C=C bond to prepare complex, value-added organosulfur products in a single step.…”