Robust N-heterocyclic carbene palladium complexes are highly efficient catalysts for direct alkylsulfonylation of (hetero)aryl- or alkenyl-boronic acids with potassium metabisulfite and (hetero)alkyl-halides. Among them, acenaphthoimidazolylidene palladium(ii) complexes exhibited the highest activities, and up to quantitative yields were obtained for diverse structurally distinct sulfones under very mild reaction conditions.
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http://dx.doi.org/10.1039/c7cc05851a | DOI Listing |
Chem Commun (Camb)
August 2024
School of Pharmaceutical and Chemical Engineering & Institute for Advanced Studies, Taizhou University, 1139 Shifu Avenue, Taizhou 318000, China.
A green process for the direct C(sp)-H decarboxylative alkylsulfonylation of enamides under metal- and additive-free conditions is reported. This reaction employs phenyliodine(III) dicarboxylates as the alkyl radical precursors and DABCO·(SO) as the sulfur dioxide surrogate. Diverse ()-alkylsulfonyl enamides are generated in moderate to good yields with high stereoselectivity under extremely mild conditions a radical process.
View Article and Find Full Text PDFJ Org Chem
April 2024
School of Pharmacy, Continuous Flow Engineering Laboratory of National Petroleum and Chemical Industry, Changzhou University, Changzhou, Jiangsu 213164, China.
General and convenient visible-light-promoted alkylsulfonylation and cyanoalkylsulfonylation of MBH adducts have been developed through the multicomponent insertion of sulfur dioxide, enabling the assembly of two C-S bonds to generate structurally diverse allylic alkylsulfones (43 examples in total). The reaction of MBH adducts with potassium alkyltrifluoroborates and 1,4-diazabicyclo[2.2.
View Article and Find Full Text PDFNat Commun
February 2024
Key Laboratory of Precision and Intelligent Chemistry and Department of Chemistry, University of Science and Technology of China, Hefei, P. R. China.
Transition metal-catalyzed reductive difunctionalization of alkenes with alkyl halides is a powerful method for upgrading commodity chemicals into densely functionalized molecules. However, super stoichiometric amounts of metal reductant and the requirement of installing a directing group into alkenes to suppress the inherent β-H elimination bring great limitations to this type of reaction. We demonstrate herein that the difunctionalization of alkenes with two different alkyl halides is accessible via a radical-anion relay with NaSO as both reductant and sulfone-source.
View Article and Find Full Text PDFChem Commun (Camb)
August 2023
School of Pharmacy, Nantong Key Laboratory of Small Molecular Drug Innovation, Nantong University, 19 Qixiu Road, Nantong 226001, China.
Photoredox alkene or alkyne alkylsulfonylation has been achieved with phthalimide esters and sulfinates providing unexpected α-sulfones. Mechanistic studies disclose that the preferential alkyl radical addition to the alkene or the Markovnikov hydrosulfonation of the alkyne should contribute to the formation of the β-alkylated α-sulfones. Moreover, the reaction is easy to operate covering quite large substrate scales including primary, secondary and tertiary alkyl groups and all sorts of terminal aryl alkenes or alkynes.
View Article and Find Full Text PDFChem Commun (Camb)
January 2021
School of Pharmaceutical and Materials Engineering & Institute for Advanced Studies, Taizhou University, 1139 Shifu Avenue, Taizhou 318000, China. and State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China and School of Chemistry and Chemical Engineering, Henan Normal University, China.
A convenient and efficient approach to (E)-alkylsulfonyl olefins via a metal/light-free three-component reaction of alkenylboronic acids, sodium metabisulfite and Katritzky salts is described. This alkylsulfonylation proceeds smoothly with a broad substrate scope, leading to diverse (E)-alkylsulfonyl olefins in moderate to good yields. During the process, excellent functional group tolerance is observed and sodium metabisulfite is used as the source of sulfur dioxide.
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