A direct one-pot alkylation-aminoxidation of styrene derivatives was achieved using -generated alkyl and -oxyl radicals. The corresponding -alkylated hydroxylamine derivatives were obtained in moderate to good yields. The reaction features the generation of the alkyl radicals from phenyliodine(III) dicarboxylates an organocatalytic process, the use of phenyliodine(III) dicarboxylates as the source of the alkyl radicals and oxidants for the generation of -oxyl radicals, and the first generation of the β-enaminyl radicals a HAT process and their use as single-electron donors.
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http://dx.doi.org/10.1039/d2ob01826h | 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 PDFOrg Biomol Chem
January 2023
Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249-069, USA.
A direct one-pot alkylation-aminoxidation of styrene derivatives was achieved using -generated alkyl and -oxyl radicals. The corresponding -alkylated hydroxylamine derivatives were obtained in moderate to good yields. The reaction features the generation of the alkyl radicals from phenyliodine(III) dicarboxylates an organocatalytic process, the use of phenyliodine(III) dicarboxylates as the source of the alkyl radicals and oxidants for the generation of -oxyl radicals, and the first generation of the β-enaminyl radicals a HAT process and their use as single-electron donors.
View Article and Find Full Text PDFMolecules
December 2020
Department of Chemistry and Biotechnology, School of Science, Tallinn University of Technology, Akadeemia tee 15, 12618 Tallinn, Estonia.
Oxidative fragmentation of tertiary cyclopropanols with phenyliodine(III) dicarboxylates in aprotic solvents (dichloromethane, chloroform, toluene) produces mixed anhydrides. The fragmentation reaction is especially facile with phenyliodine(III) reagents bearing electron-withdrawing carboxylate ligands (trifluoroacetyl, 2,4,6-trichlorobenzoyl, 3-nitrobenzoyl), and affords 95-98% yields of the corresponding mixed anhydride products. The latter can be straightforwardly applied for the acylation of various nitrogen, oxygen and sulfur-centered nucleophiles (primary and secondary amines, hydroxylamines, primary alcohols, phenols, thiols).
View Article and Find Full Text PDFOrg Lett
July 2020
Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry & Molecular Engineering, East China University of Science and Technology, 130 Mei Long Road, Shanghai 200237, People's Republic of China.
A visible-light-mediated decarboxylative tandem carbocyclization of acrylamide-tethered alkylidenecyclopropanes with phenyliodine(III) diacetate and various aliphatic acids has been reported in this paper. An alkyl radical in situ generated from phenyliodine(III) dicarboxylates upon visible-light irradiation catalyzed by -Ir(ppy) adds to the less hindered central carbon of alkylidenecyclopropane to initiate the tandem annulation, generating tetracyclic benzazepine derivatives in moderate to good yields with broad substrate scope under mild conditions.
View Article and Find Full Text PDFOrg Biomol Chem
July 2019
College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, 730070, P. R. China. and State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, P. R. China.
A simple and efficient method for the visible light induced direct carbon alkylation of quinoxalin-2(1H)-ones at the C3 position is described. This protocol employs cheap and readily available phenyliodine(iii) dicarboxylates as the alkylation reagents to conduct decarboxylative radical coupling reaction with quinoxalin-2(1H)-ones. The process exhibits excellent compatibility to functional groups and provides a convenient and selective access to various 3-alkylquinoxalin-2(1H)-ones in good yields.
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