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Selectfluor, [1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate)], is a highly valuable reagent in contemporary chemistry, serving not only as an electrophilic fluorinating agent but also as an effective catalyst in the synthesis of various pharmaceutically relevant heterocycles. This review article seeks to present a comprehensive overview of the significant heterocyclic ring formations facilitated by selectfluor. Both metal-free and metal-catalyzed recent advancement on selectfluor mediated cyclisation processes are discussed in this review mainly over last eight years (2017-April 2024).
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http://dx.doi.org/10.1002/tcr.202400216 | DOI Listing |
Org Biomol Chem
August 2025
School of Pharmacy, Xinxiang University, Xinxiang, Henan 453000, P. R. of China.
The three-component reaction offers a convenient method for synthesizing difluorinated compounds. In this review, we classify and discuss synthetic methodologies developed over the past decade (2014-2024) into three categories: (a) radical reactions, (b) difluorocarbene-mediated fluorination, and (c) other reaction types, including those using nucleophilic and electrophilic fluorine reagents. Various reagents such as AgF, pyridine·9HF, Selectfluor II, TMSCF, TMSCFBr, TMSCFPO(OEt), RCF, (CFCO)O, ClCFH, ClCFCONa, CFHSONa, [PhPCFH]Br, ClCFCl, BrCFR, ICFCOAr, and BrCFCOEt will be discussed.
View Article and Find Full Text PDFChem Rec
April 2025
Department of Chemistry, Jadavpur University, 188, Raja Subodh Chandra Mallick Rd, Jadavpur, Kolkata, West Bengal, 700032, India.
Selectfluor, [1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate)], is a highly valuable reagent in contemporary chemistry, serving not only as an electrophilic fluorinating agent but also as an effective catalyst in the synthesis of various pharmaceutically relevant heterocycles.
View Article and Find Full Text PDFOrg Lett
November 2024
Graduate School of Pharmaceutical Sciences, Kyoto University, Sakyo, Kyoto 606-8501, Japan.
A metal-free and mild cleavage of tertiary -methoxybenzyl amides (PMB -amide) under photoredox conditions is developed using Mes-Acr-PhBF and Selectfluor to activate the electron-rich benzylic C-H bond of the PMB moiety. The resulting acyl fluoride intermediate is versatile and facilitates a one-pot transamidation of the PMB -amide. The value of this protocol is highlighted by performing the chemoselective activation of the PMB -amide in bifunctional molecules containing more reactive functionalities than the amide.
View Article and Find Full Text PDFOrg Lett
September 2024
Graduate School of Pharmaceutical Sciences, Kyoto University, Sakyo, Kyoto 606-8501, Japan.
A new strategy for the metal-free photoinduced activation of -methoxybenzyl esters is developed using Selectfluor and benzil for the generation of acyl fluoride intermediates that enable various transformations. The highlight of this activation method is its high chemoselectivity in the presence of other functionalities, such as esters, amides, and ketones. A synthetic application for the preparation of peptide mimetics that possess two different amide units is also described.
View Article and Find Full Text PDFChem Commun (Camb)
October 2024
State Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development; School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200062, P. R. China.
Chiral organofluorine compounds featuring a monofluoromethyl (CHF)-substituted stereocenter are often encountered in a number of drugs and bioactive molecules. Consequently, the development of catalytic asymmetric methods for the enantioselective construction of CHF-substituted stereocenters has made great progress over the past two decades, and a variety of enantioselective transformations have been accordingly established. According to the types of fluorinated reagents or substrates employed, these protocols can be divided into the following major categories: (i) enantioselective ring opening of epoxides or azetidinium salts by fluoride anions; (ii) asymmetric monofluoromethylation with 1-fluorobis(phenylsulfonyl)methane; (iii) asymmetric fluorocyclization of functionalized alkenes with Selectfluor; and (iv) asymmetric transformations involving α-CHF ketones, α-CHF alkenes, or other CHF-containing substrates.
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