A general and facile synthetic method for C(sp)-H difluoroalkylations and perfluoroalkylations of alkenes and (hetero)arenes with commercially available fluoroalkyl halides has been developed with a copper-amine catalyst system. This method is characterized by high yields, mild reaction conditions, low-cost catalyst, broad substrate scope, and excellent functional group compatibility, therefore providing a convenient synthetic strategy toward various difluoroalkyl- and perfluoroalkyl-substituted alkenes and (hetero)arenes.
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http://dx.doi.org/10.1021/acs.orglett.7b01712 | DOI Listing |
Org Lett
January 2025
Department of Chemistry, University of Hawai'i at Ma̅noa, Honolulu, Hawaii 96822, United States.
We present a photocatalytic method for alkylamination of alkenes, enabling efficient C-C and C-N bond formation to construct aza-heterocycles valuable in drug discovery. Using a radical-polar crossover pathway, electron-deficient alkenes are reduced to electrophilic radicals, which react with electron-rich alkenes to form nucleophilic radicals. Oxidation of these intermediates yields carbocations, which are trapped by aza-heteroarenes to afford alkylaminated products.
View Article and Find Full Text PDFAcc Chem Res
January 2025
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, and Discipline of Intelligent Instrument and Equipment, Xiamen University, Xiamen 361005, P. R. China.
ConspectusMolecular photoelectrocatalysis, which combines the merits of photocatalysis and organic electrosynthesis, including their green attributes and capacity to offer novel reactivity and selectivity, represents an emerging field in organic chemistry that addresses the growing demands for environmental sustainability and synthetic efficiency. This synergistic approach permits access to a wider range of redox potentials, facilitates redox transformations under gentler electrode potentials, and decreases the use of external harsh redox reagents. Despite these potential advantages, this area did not receive significant attention until 2019, when we and others reported the first examples of modern molecular photoelectrocatalysis.
View Article and Find Full Text PDFNat Commun
January 2025
Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 200032, Shanghai, China.
Considering the unique electronic properties of the CF and the CN groups, the CFCN group has significant potential in drug and agrochemical development, as well as material sciences. However, incorporating a CFCN group remains a considerable challenge. In this work, we disclose a use of bromodifluoroacetonitrile (BrCFCN), a cost-effective and readily available reagent, as a radical source for cyanodifluoromethylation of alkyl alkenes, aryl alkenes, alkynes, and (hetero)arenes under photocatalytic conditions.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
College of Materials, Chemistry & Chemical Engineering, Chengdu University of Technology, Chengdu 610059, China.
Due to the special structure and physicochemical properties of sulfoximines, research on sulfoximines has achieved great progress in recent decades, especially in chemical and medicinal fields. This review highlights recent advancements in the N-functionalization of NH-sulfoximines, focusing on classical cross-coupling reactions with electrophilic agents and oxidative coupling reactions with extensive organic compounds, including specific (hetero)arenes, alkenes (1,4-naphthoquinones), alkanes (cyclohexanes), nucleophiles (thiols, disulfides, sulfinates, diarylphosphine oxides), organyl boronic acids, and arylhydrazines. Transition metal-catalyzed, metal-free, electrochemical and radical oxidative coupling reactions are discussed.
View Article and Find Full Text PDFJ Org Chem
January 2025
Department of Chemistry, 107 Physical Sciences, Oklahoma State University, Stillwater, Oklahoma 74078, United States.
Fused heterocyclic scaffolds, such as benzimidazoles or larger ring systems containing a benzimidazole fragment, are frequently encountered in pharmaceutical compounds and other biologically active molecules. While there are many examples of N9- and/or C3-substituted 9-benzo[4,5]imidazo[2,1-][1,2,4]triazoles, current examples of the regioselective preparation of N1-substituted 1-benzo[4,5]imidazo[2,1-][1,2,4]triazoles are limited to N1-aryl substituted compounds, which also contain a C3-substituent. Here, we report an iodine-promoted C-H bond amination reaction that allows the selective preparation of 1-benzo[4,5]imidazo[2,1-][1,2,4]triazoles with a variety of aryl and alkyl N1-substituents.
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