Synthesis of (Bromodifluoromethyl)trimethylsilane and Its Applications in Organic Synthesis

Chinese Journal of Organic Chemistry, Год журнала: 2023, Номер 43(10), С. 3491 - 3491

Опубликована: Янв. 1, 2023

Bromodifluoromethyl trimethylsilane (TMSCF2Br) has proved to be an important difluoromethyl(alkyl)ation reagent that is widely applied in organic synthesis over the past decade, since it was used as a difluorocarbene precursor 2011.This review aims provide briefly summary for of TMSCF2Br, and introduce recent advances applications TMSCF2Br or trimethylsilyldifluoromethyl radical developing various difluoromethyl(alkyl)ations different kinds substrates.Meanwhile, activation ways possible mechanism, well its advantages disadvantages each kind reactions are detailedly disccussed, which might some references inspiration researchers engaged fluorine chemistry.

Язык: Английский

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TMSCF₂Br‐Enabled Fluorination–Aminocarbonylation of Aldehydes: Modular Access to α‐Fluoroamides

Angewandte Chemie, Год журнала: 2021, Номер 134(8)

Опубликована: Дек. 16, 2021

Abstract A protocol for the modular assembly of α‐fluoroamide motif has been developed, which provides a practical method efficient synthesis structurally diverse α‐fluoroamides from easily available aldehydes and tertiary amines through three‐component fluorination–aminocarbonylation process. The key to success this process is taking advantage multiple roles unique difluorocarbene reagent TMSCF 2 Br (TMS=trimethylsilyl). mechanism involves 1,2‐fluorine oxygen migrations in situ formed TMS‐protected α‐aminodifluoromethyl carbinol intermediates, represents new type deoxyfluorination reaction.

Язык: Английский

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Controllable Double Difluoromethylene Insertions into S−Cu Bonds: (Arylthio)tetrafluoroethylation of Aryl Iodides with TMSCF₂Br

Angewandte Chemie, Год журнала: 2024, Номер 136(14)

Опубликована: Фев. 15, 2024

Abstract A new method of constructing “ArSCF 2 CF Cu” from ArSCu and TMSCF Br (TMS=trimethylsilyl) has been developed. The cross‐coupling reactions the obtained with diverse aryl iodides (Ar′I) provide an efficient access to Ar′CF SAr. Mechanistic studies demonstrate that species were generated through controllable double difluoromethylene insertions into ArS−Cu bonds rather than 1,2‐addition tetrafluoroethylene.

Язык: Английский

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Difluorocarbene in Cycloadditions and Annulations for the Synthesis of gem‐Difluorocarbocycles and gem‐Difluoroheterocycles

European Journal of Organic Chemistry, Год журнала: 2023, Номер 27(3)

Опубликована: Ноя. 13, 2023

Abstract Difluorocarbene is a simple, readily prepared, and versatile difluorinated one‐carbon synthon. It can be applied as both the difluoromethylating reagent in carbene insertion difluoromethylenating various cycloadditions annulations. This concept article provides an account of applications difluorocarbene annulations for synthesis gem ‐difluorocarbocycles ‐difluoroheterocycles. The synthesized include 2,2‐difluorobicyclo[1.1.1]pentanes, 4,4‐/5,5‐difluoro‐cyclopentenes, 2,2‐difluorocyclopentanones, 5,5‐difluorocyclopent‐2‐enones via tandem [2+1] cycloaddition ring‐expansion or [4+1] prepared ‐difluoroheterocycles involve 2,2‐/3,3‐difluoro‐2,3‐dihydrofurans, 2,2‐difluoro‐2,3‐dihydrobenzofurans, 2,2‐difluoro‐2,3‐dihydrobenzothiophenes, 2,2‐difluorobenzofuran‐3(2 H )‐ones, 2,2‐difluorobenzothiophen‐3(2 2,2‐difluoro‐2,3‐dihydrothieno[2,3‐ b ]pyridines, 2,2‐difluorothieno[2,3‐ ]pyridine‐3(2 5,5‐difluorooxazolines thiazolines, spirocyclic 2,2‐difluorobenzo[ d ][1,3]aza/phosphaborol‐1‐ium‐3‐yliums annulations, 1,1‐difluoro‐1,4,5,9b‐tetrahydro‐2 ‐[1,2]diazeto[4,1‐ ]isoquinolines ‐[1,2]diazeto[1,4‐ ]pyrrolo[2,1‐ c ]pyrazines [3+1] annulation, 1,1‐difluoro‐1,9a‐dihydropyrido[2,1‐ ][1,4]thiazines 3,3‐difluorobenzo[ e ][1,4,2]oxaza/phosphaborinin‐4‐ium‐2‐uides [5+1] 9,9‐difluoro‐8‐azabicyclo[5.2.0]nona‐2,4,6‐trienes [8+1] 4,4‐difluorooxazolidines 3,3‐difluoropyrrolidines [2+2+1] generated from different available precursors proceeds these well. substrate scopes, proposed mechanisms, selected product examples their are discussed.

Язык: Английский

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Five-membered ring systems: pyrroles and benzo analogues

Progress in heterocyclic chemistry, Год журнала: 2021, Номер unknown, С. 119 - 173

Опубликована: Янв. 1, 2021

Язык: Английский

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