Alkenyl sulfides have gained increasing prominence in medicinal chemistry and materials. Hydrothiolation of alkynes for the diverse synthesis of alkenyl sulfides is an appealing method. Herein, we report a cobalt-catalyzed Markovnikov hydromethylthiolation of alkynes to afford branched alkenyl methylsulfanes with good yields and high regioselectivity. This method also enables the diverse synthesis of branched alkenyl sulfides. The reaction shows good functional group tolerance and could be scaled up. The mechanistic studies including control experiments, deuterium-labeling experiments, and Hammett plot indicated alkynes insertion followed by electrophilic thiolation pathway.
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http://dx.doi.org/10.1038/s41467-024-52249-x | DOI Listing |
Nat Commun
November 2024
Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, International Innovation Center for Forest Chemicals and Materials, Nanjing Forestry University, Nanjing, 210037, China.
Cyclopropanes are not only privileged motifs in many natural products, agrochemicals, and pharmaceuticals, but also highly versatile intermediates in synthetic chemistry. As such, great effort has been devoted to the cyclopropane construction. However, novel catalytic methods for cyclopropanation with two abundant substrates, mild conditions, high functional group tolerance, and broad scope are still highly desirable.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2024
Key Laboratory of Molecule Synthesis and Function Discovery, Fujian Province University, College of Chemistry at Fuzhou University, Fuzhou, Fujian, 350108, China.
Zweifel reaction is a powerful strategy to construct olefins from alkenyl tetracoordinate borons in organoboron chemistry, however, it usually only involves one functional group migration and then undergoes an elimination process affording alkenes or alkynes exclusively. Herein, we disclose several intriguing interception of alkynyl tetracoordinate borons with sulfur electrophiles. Wherein, the substituted benzothiophenes are accessed by consecutive 1,2-migrations and intramolecular electrophilic substitution, meanwhile, the challenging and elusive five/four-membered boracycles are easily assembled, and an approach to alkenyl sulfides with good stereoselectivity was developed as well.
View Article and Find Full Text PDFNat Commun
September 2024
Center of chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou, 310058, China.
Alkenyl sulfides have gained increasing prominence in medicinal chemistry and materials. Hydrothiolation of alkynes for the diverse synthesis of alkenyl sulfides is an appealing method. Herein, we report a cobalt-catalyzed Markovnikov hydromethylthiolation of alkynes to afford branched alkenyl methylsulfanes with good yields and high regioselectivity.
View Article and Find Full Text PDFACS Catal
February 2024
Department of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, U.K.
Functionalized sulfides are important in many areas of science, ranging from chemical biology through drug discovery to organic materials chemistry. Sulfides bearing pendant reactive groups in the α-position are particularly useful; however, methods for the selective valorization of simple sulfides or the late-stage functionalization of complex sulfides by the convenient addition of valuable functionality are underexplored. Here we exemplify a general reaction platform for sulfide functionalization by showcasing three modes of α-sulfur C-H functionalization; cyanation, alkenylation, and alkynylation.
View Article and Find Full Text PDFFood Res Int
February 2024
Plant Quality and Food Security, Leibniz Institute of Vegetable and Ornamental Crops (IGZ) e.V., Theodor-Echtermeyer-Weg 1, 14979 Grossbeeren, Germany; Leibniz Institute of Vegetable and Ornamental Crops (IGZ) e. V., Theodor-Echtermeyer-Weg 1, 14979 Grossbeeren, Germany. Electronic address:
Cabbages are rich in sulfur-containing metabolites like glucosinolates (GLSs) and S-methyl-l-cysteine sulfoxide (SMCSO). Tissue disruption initiates hydrolysis of these compounds and bioactive volatile hydrolysis products such as isothiocyanates (ITCs), sulfides, and thiosulfinates are formed. However, nitriles, epithionitriles, or amines can also result from GLSs.
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