We report herein a practical method to generate CFSe (and RSe) anions from shelf-stable reagents under iodide activation. Metal-free nucleophilic trifluoromethylselenolations have been then performed with this in situ-generated anion. Perfluoroalkylselenolations have also been described.
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http://dx.doi.org/10.3762/bjoc.16.252 | DOI Listing |
Angew Chem Int Ed Engl
December 2024
University of Ottawa, Department of Chemistry and Biomolecular Sciences, 10 Marie Curie, k1n6n5, Ottawa, CANADA.
Hydrosilanes and Lewis bases are known to promote various reductive defunctionalizations, rearrangements, and silylation reactions, facilitated by enigmatic silicon/Lewis base-derived reactive intermediates. Despite the wide variety of transformations enabled by this reagent combination, no examples of intermolecular C(sp3)-C(sp3) forming reactions have been reported. In this work, we've identified 1,1,3,3-tetramethyldisiloxane (TMDSO) and KOtBu as a unique reagent combination capable of generating benzylic nucleophiles in-situ from styrene derivatives, which can subsequently react with alkyl halides to give a new C(sp3)-C(sp3) linkage via formal hydroalkylation.
View Article and Find Full Text PDFFront Chem
November 2024
Endocrinology and Metabolism Research Center, Endocrinology and Metabolism Clinical Sciences Institute, Tehran University of Medical Sciences, Tehran, Iran.
Introduction: The increasing prevalence of antibiotic-resistant pathogens necessitates the urgent development of new antibacterial agents. Concurrently, synthetic chemistry is moving towards more sustainable practices that minimize environmental impact. This study aims to synthesize 3-aryl-2-benzo[b][1,4]oxazin-2-one derivatives, including the natural product cephalandole A, using a sustainable approach that avoids metal catalysts.
View Article and Find Full Text PDFOrg Biomol Chem
December 2024
Natural Product and Medicinal Chemistry Division, CSIR-Indian Institute of Integrative Medicine, Jammu-180001, India.
Dalton Trans
December 2024
Department of Chemistry, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110 016, India.
Carbenes in general and isolable NHCs (N-heterocyclic carbenes) in particular have been useful ligands in recent years. The emergence of CAACs [cyclic(alkyl)(amino)carbenes], BICAACs [bicyclic(alkyl)(amino)carbenes], and many other carbenes has marked revolutionary milestones in this field. These carbenes possess an intriguing blend of highly electrophilic and nucleophilic characteristics, owing to their remarkably narrow HOMO-LUMO energy gap.
View Article and Find Full Text PDFChemistry
November 2024
Department of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK.
We report the development of an azanide (NH) surrogate which enables the facile conversion of electron-deficient (hetero)aryl halides into primary N-aryl amines under transition-metal-free conditions. The designed amidine reagent is easy to prepare, bench stable, and undergoes facile N-arylation under basic conditions at 40 °C. Intermediate N-aryl amidines are readily cleaved to form N-aryl amines in situ through hydrolysis or base-promoted elimination.
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