Article
Chemistry, Organic
Chen-Yuan Li, Zengyu Zhang, Xiaoyu Yan
Summary: This study presents a novel strategy for postmodification of difluoromethyl compounds. Ortho-selective C-H borylation of difluoromethyl arenes is achieved by a cyclometalated mesoionic carbene-Ir complex. The regioselectivity is controlled by a hydrogen bond between CF2H and the boryl group via the outer-sphere direction.
Article
Chemistry, Multidisciplinary
Tao Huang, Yuan-Yuan Zong, Tao Huang, Xiao-Ling Jin, Li-Zhu Wu, Qiang Liu
Summary: Visible-light-promoted site-selective and direct C-F bond functionalization of polyfluorinated iminosulfides allows the synthesis of gamma-lactams with a fluoro- and perfluoroalkyl-substituted carbon centre. The reaction shows high chemoselectivity control and excellent functional group tolerance.
Article
Chemistry, Organic
Haijian Wu, Peng Hong, Wenxue Xi, Jinshan Li
Summary: A new efficient [2 + 3] cyclization method using difluoroenoxysilanes and p-hydroxybenzyl alcohols has been developed to synthesize highly functionalized gem-difluorinated oxa-spirocyclohexadienones under mild conditions.
Article
Chemistry, Organic
Wen-Jun Yue, Craig S. Day, Adrian J. Brenes Rucinski, Ruben Martin
Summary: We present a modular catalytic technique that simplifies the preparation of gem-difluoroalkanes from unactivated sp3 precursors. This method exhibits simplicity, generality, and site selectivity, allowing for the functionalization of advanced intermediates and olefin feedstocks. Our strategy involves a cooperative interplay of halogen- and hydrogen-atom transfer, providing a new entry point to difluorinated alkyl bioisosteres of interest in drug discovery.
Article
Chemistry, Multidisciplinary
Haiwei Zhao, Xuebing B. Leng, Wei Zhang, Qilong Shen
Summary: The discovery of a powerful difluoromethylating reagent [Ph4P](+)[Cu(CF2H)(2)](-) 2 was made in the quest for active species in copper-mediated difluoromethylation of aryl halides. Complex 2 was able to difluoromethylate a variety of electrophiles including aryl halides, arylboronic acid pinacol esters, alkynes, and heteroarenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Joseph Ford, Benjamin Hopkin, Jeroen B. I. Sap, Veronique Gouverneur
Summary: We report a simplified protocol for solvent-free, mechanochemical difluoromethylation using non-ozone depleting chlorodifluoromethyl phenyl sulfone as a difluorocarbene source. The protocol demonstrates a short reaction time, excellent functional group tolerance, and compatibility with complex biologically active scaffolds.
ISRAEL JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Organic
Nai-Chen Hsueh, Meng-Yang Chang
Summary: This study demonstrates the one-pot tandem cyclocondensation reaction of 1,3-bis-sulfonylpropan-2-ones with arylaldehydes, mediated by piperidinium acetate, to produce tris-sulfonyl 3-arylphenols. The reaction proceeds under easy-operational conditions and generates water and sulfinic acid as byproducts.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Review
Chemistry, Physical
Pravya P. Nair, Rose Mary Philip, Gopinathan Anilkumar
Summary: The importance of fluorine in the pharmaceutical and agrochemical industry has led to increased attention on methods to introduce fluorine into compounds. Nickel catalysts have shown promising applications in introducing various fluorinated functionalities, and this review comprehensively covers the strategies and mechanistic analyses involved in nickel-catalysed fluoromethylation reactions up to 2021.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)
Article
Chemistry, Multidisciplinary
Mark W. Campbell, Viktor C. Polites, Shivani Patel, Juliette E. Lipson, Jadab Majhi, Gary A. Molander
Summary: A photochemically mediated method has been successfully developed for the defluorinative alkylation of ethyl trifluoroacetate, providing an efficient pathway for the synthesis of novel gem-difluoro analogs. This method can also be used for the hydroalkylation of a diverse suite of alkenes, expanding the range of substrates for the reaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Cheng Wu, Xiao Shen, Jianjun Dai, Jun Xu, Huajian Xu
Summary: By utilizing a direct nucleophilic substitution reaction under transition metal free conditions, easily available aryl and alkyl thiocyanates were converted into the desired products, enabling the synthesis of (benzenesulfonyl)difluoromethyl thioethers.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Materials Science, Multidisciplinary
Sijia Huang, Steven M. Adelmund, Pradip S. Pichumani, Johanna J. Schwartz, Yigit Menguc, Maxim Shusteff, Thomas J. Wallin
Summary: Seamless multimaterial construction is common in animal physiology but difficult to reproduce in engineered systems. This study introduces a photothermal reaction scheme that can produce multimaterials by altering the microstructure of a single resin, resulting in a diverse range of mechanical properties and modulus gradients.
Article
Chemistry, Organic
Bei Zhang, Jian Wang
Summary: In this study, a new acyldifluoromethylation reaction has been reported, which achieves efficient synthesis on inert alkenes through synergistic catalysis. The method exhibits a broad substrate scope and good functional group tolerance.
Article
Chemistry, Organic
Ran Liu, Jinbo Hu
Summary: In this study, aryl perfluorocyclopropyl ethers were synthesized for the first time via a [2 + 1] cyclopropanation reaction between aryl trifluorovinyl ethers and TMSCF2Br reagent. The reaction proceeded smoothly under suitable conditions and demonstrated tolerance to various functional groups.
Article
Engineering, Environmental
Xiaoyang Li, Xinyu Hu, Yida Qiao, Tianying Lu, Yunxiu Bai, Jiarong Xiong, Xinyang Li, Qingqiang Gou, Jun Ge
Summary: By constructing an enzyme-bimetallic hybrid catalyst on cross-linked lipase aggregates, the intrinsic incompatibility between enzyme and chemical catalysts in one-pot chemoenzymatic cascade reactions was overcome, resulting in improved activity and lower reaction temperature.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Biochemistry & Molecular Biology
Qinghe Liu, Taige Kong, Chuanfa Ni, Jinbo Hu
Summary: A reagent-controlled highly stereoselective reaction was reported for the synthesis of enantiomerically enriched alpha-difluoromethyl amines using (S)-difluoromethyl phenyl sulfoximine 1 and imines. This approach offers high efficiency, high stereoselectivity, and a broad substrate scope, possibly achieved through a non-chelating transition state.
