Synthetic and mechanistic aspects of the reactions between bromodifluoromethyltriphenylphosphonium bromide and dibromofluoromethyltriphenylphosphonium bromide and trialkylphosphites

Flynn, Richard M.; Burton, Donald J.; Wiemers, Denise M.

doi:10.1016/j.jfluchem.2008.04.003

Cited by 12 publications

(3 citation statements)

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“…Phosphoryldifluoromethylation of ketones with Me 3 SiCF 2 P(O)(OEt) 2 , in contrast with aldehydes, [37,118,137] remained scarcely explored until the recent report by Zhou and co‐workers [138] . They showed that by using KOAc/18‐crown‐6 system as the reaction promoter [139] instead of conventional F − or AlkO − bases, it was possible to suppress the phosphonate‐phosphate rearrangement usually observed when a stronger base was used [140] and isolate the corresponding α,α‐difluoro‐β‐silyloxyphosphonates 85 in 33–83% yields (Scheme 36).…”

Section: Synthetic Methodsmentioning

confidence: 99%

Recent Advances in Synthesis of Difluoromethylene Phosphonates for Biological Applications

et al. 2021

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For almost 40 years, difluoromethylene phosphonates have proven to be versatile molecular tools in biochemical studies owing to their close resemblance to naturally occurring phosphates and phosphonates. As bioisosteric, non‐hydrolyzable analogs of these essential molecules, difluoromethylene phosphonates can target the critical parts of the cellular machinery and therefore exhibit a diverse spectrum of biological activity. In the past ten years, there have appeared many new methods for the synthesis of difluoromethylene phosphonates. Most notably, photoredox catalysis has firmly entered the field, while cross‐coupling and nucleophilic strategies have met considerable elaboration and refinement, entirely in accord with the current trends in synthetic organic chemistry. Herein, we introduce difluoromethylene phosphonates as a distinct, high‐tech subclass of synthetic phosphonates resulting from the research efforts on the cross‐section of organophosphorus, organofluorine, and bioorganic chemistry. We then proceed to the discussion of general methods for the preparation of difluoromethylene phosphonates, comprehensively reviewing reactions developed in the past 15 years while providing the context of earlier works where appropriate. Finally, we present selected examples of molecules with high biological activity, their biological targets, and the synthetic steps employed for their preparation.

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Section: Synthetic Methodsmentioning

confidence: 99%

Recent Advances in Synthesis of Difluoromethylene Phosphonates for Biological Applications

et al. 2021

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“…Qing and co‐workers developed a methodology for visible light‐driven hydro‐difluoromethylation of alkenes ( 62 ) with the easy‐to‐handle (bromodifluoromethyl)triphenylphosphonium bromide [(Ph 3 PCF 2 Br) + Br − ] for the insertion of CF 2 H groups, in the presence of H 2 O and THF . The reagent (Ph 3 PCF 2 Br) + Br − was recognized exclusively as a difluorocarbene precursor . Nevertheless, the authors found that (Ph 3 PCF 2 Br) + Br − can be implemented as a CF 2 Br donor, under visible light irradiation.…”

Section: General Introductionmentioning

confidence: 99%

Progress in Difluoroalkylation of Organic Substrates by Visible Light Photoredox Catalysis

2019

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Thes electivei ncorporation of fluorinated motifs, in particularC F 2 FG (FG = af unctional group) and CF 2 Hg roups,i ntoo rganic compounds has attrracted increasing attention since organofluorine molecules are of the utmost importance in the areas of nuclear imaging,pharmaceutical, agrochemical, and material sciences.Avariety of synthetic approachesh as been employed in late-stage difluoroalkylationr eactions.V isible light photoredox catalysis for the production of CF 2 FG and CF 2 Hr adicalsh as providedamore sustainable alternative to other conventional radical-triggered reactions from the viewpoint of safety,c ost, availability,a nd "green"c hemistry.Awide range of difluoroalkylating reagents has been successfully implemented in these organic transformationsi nt he presence of transitionm etal complexes or organic photocatalysts.I nmost cases, upon excitation via visible light irradiation with fluorescent light bulbs or blue light-emitting diode (LED) lamps,t hese photocatalysts can act as both reductivea nd oxidative quenchers,t hus enabling the applicationo fe lectron-donoro re lectron-acceptor difluoroalkylating reagents for the generation of CF 2 FG andC F 2 Hr adicals.S ubsequent radical addition to substrates and additional organic transformations affordt he corresponding difluoroalkylatedd erivatives.T he presentr eview describes the distinct strategies for the transitionm etal-and organic-pho-tocatalyzed difluoroalkylation of ab road range of organic substrates by visible light irradiationr eported in the literature since 2014.

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“…Known reagent preparations have not included such variability, with scope limited to −OEt and −O i -Pr derivatives. Despite the associated hazards, limited availability, and requirement of an additional silylation step, they are accessed from the controlled substance CF 2 Br 2 (Halon 1202): a class I ozone depleting substance and the most hazardous fluorobromocarbon known. Another approach involves C(sp 3 )–H chlorination of diisopropyl ((methylthio)methyl)phosphonate, chlorine-fluorine exchange (with 3HF-Et 3 N), activation with n -BuLi, and silylation (Figure ).…”

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Siladifluoromethylation and Deoxo-trifluoromethylation of P^V–H Compounds with TMSCF₃: Route to P^V–CF₂^– Transfer Reagents and P–CF₃ Compounds

2019

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A method for siladifluoromethylation of dialkyl phosphonates and secondary phosphine oxides with TMSCF3 to produce nucleophilic PV–CF2– transfer reagents is disclosed, with multigram scale reactions included. Condition-dependent divergent reactivity under the established conditions is demonstrated by the formation of trifluoromethylphosphines. Both one-pot transformations are operationally simple and employ inexpensive materials. Mechanistic investigations suggest the divergent reactivity originates from a common intermediate, with Li+ concentration directing the chemoselectivity.

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Synthetic and mechanistic aspects of the reactions between bromodifluoromethyltriphenylphosphonium bromide and dibromofluoromethyltriphenylphosphonium bromide and trialkylphosphites

Cited by 12 publications

References 13 publications

Recent Advances in Synthesis of Difluoromethylene Phosphonates for Biological Applications

Recent Advances in Synthesis of Difluoromethylene Phosphonates for Biological Applications

Progress in Difluoroalkylation of Organic Substrates by Visible Light Photoredox Catalysis

Siladifluoromethylation and Deoxo-trifluoromethylation of P^V–H Compounds with TMSCF₃: Route to P^V–CF₂^– Transfer Reagents and P–CF₃ Compounds

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Synthetic and mechanistic aspects of the reactions between bromodifluoromethyltriphenylphosphonium bromide and dibromofluoromethyltriphenylphosphonium bromide and trialkylphosphites

Cited by 12 publications

References 13 publications

Recent Advances in Synthesis of Difluoromethylene Phosphonates for Biological Applications

Recent Advances in Synthesis of Difluoromethylene Phosphonates for Biological Applications

Progress in Difluoroalkylation of Organic Substrates by Visible Light Photoredox Catalysis

Siladifluoromethylation and Deoxo-trifluoromethylation of PV–H Compounds with TMSCF3: Route to PV–CF2– Transfer Reagents and P–CF3 Compounds

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Siladifluoromethylation and Deoxo-trifluoromethylation of P^V–H Compounds with TMSCF₃: Route to P^V–CF₂^– Transfer Reagents and P–CF₃ Compounds