A novel method for the synthesis of vinyl sulfides by the decarboxylative cross-coupling of arylpropiolic acids with thiols using copper(I) salts as catalysts has been developed. In the presence of CuI and Cs(2)CO(3), a variety of thiols reacted with arylpropiolic acids to afford the corresponding vinyl sulfides in good to excellent yields with high stereoselectivity for Z-isomers.
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http://dx.doi.org/10.1021/ol101729k | DOI Listing |
J Org Chem
January 2025
Institute of Materia Medica, School of Pharmaceutical Sciences, Nanjing Tech University, Nanjing 211816, P. R. China.
In this study, we present a novel catalyst-free energy transfer mediated radical rearrangement strategy for the aryl-heterofunctionalization of unactivated alkynes, leading to the synthesis of polyfunctional olefins with exceptional stereoselectivity. This innovative approach, driven by visible light, exemplifies green chemistry principles by eliminating the reliance on transition metals, external oxidants, and photocatalysts. The broad applicability of our method is demonstrated through the successful synthesis of a diverse array of compounds, including vinyl sulfones, vinyl selenides, and vinyl sulfides.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Laboratory of Catalysis and Organic Synthesis, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne, CH-1015, Lausanne, Switzerland.
The azidofunctionalization of alkenes under mild conditions using commercially available starting materials and easily accessible reagents is reported based on a radical-polar crossover strategy. A broad range of alkenes, including vinyl arenes, enamides, enol ethers, vinyl sulfides, and dehydroamino esters, were regioselectively functionalized with an azide and nucleophiles such as azoles, carboxylic acids, alcohols, phosphoric acids, oximes, and phenols. The method led to a more efficient synthesis of 1,2-azidofunctionalized pharmaceutical intermediates when compared to previous approaches, resulting in both reduction of step count and increase in overall yield.
View Article and Find Full Text PDFJACS Au
December 2024
Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
We present a new type of elementoboration reaction, the thioboration of terminal alkynes. This method enables highly controllable regio-/stereo-/chemoselective - and -thioboration on demand, affording synthetically versatile and densely functionalized vinyl boron/vinyl sulfide derivatives in a straightforward manner without the need for a transition-metal catalyst.
View Article and Find Full Text PDFChemistry
December 2024
Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Translational Research Hub, Maindy Road, Cathays, Cardiff, Cymru/Wales, CF24 4HQ, UK.
Precise control of selective alkene functionalization is a continuing challenge in the chemical community. In this study, we develop a substitution-controlled regiodivergent thioetherification of di- or trisubstituted alkenes using 10 mol % tris(pentafluorophenyl)borane [B(CF)] as a catalyst and N-thiosuccinimide as a sulfenylating reagent. This metal-free borane catalyzed C-S bond forming method is utilized for a Csp-H sulfenylation reaction to synthesize an array of diphenylvinylsulfide derivatives with good to excellent yields (25 examples, up to 91 % yield).
View Article and Find Full Text PDFJ Org Chem
December 2024
College of Chemical Engineering, Inner Mongolia University of Technology, Hohhot 010051, China.
In this report, we have established a novel and efficient method for selectively synthesizing either vinyl sulfides or 2-methylbenzothiazoles from the reaction of CaC and disulfides. The selective synthesis of these two distinct products can be controlled by simply adjusting the amount of KS. The underlying reaction mechanism has been thoroughly investigated through control experiments, HRMS, and FTIR, which collectively support the pivotal role of a trisulfur radical anion.
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