A Facile Synthesis of 1,1-Difluoroallenes from Commercially Available 1,1,1-Trifluoro-2-iodoethane

1,1-Difluoroallenes are synthesized in good yield via zinc-promoted 1,2-elimination of 3,3-difluoro-2-iodoallylic acetates, which are prepared by the reaction of aldehydes or ketones with 1-iodo-2,2-difluorovinyllithium, generated from commercially available 1,1,1-trifluoro-2-iodoethane.Key word

Facile Synthesis of Substituted 1,1-Difluoroallenes via Carbonyl Difluorovinylidenation

Two methods for the difluorovinylidenation of carbonyl compounds have been developed to synthesize 1,1-difluoroallenes bearing various substituents. The reaction of 1-bromo-2,2-difluorovinyllithium, generated from 1,1-dibromo-2,2-difluoroethylene and n-butyllithium, with aldehydes or ketones, and subsequent acetylation, gives 2-bromo-3,3-difluoroallylic acetates. Elimination of these acetates with n-butyllithium affords 1,1-difluoroallenes in high yield. 3,3-Difluoro-2-iodoallylic acetates are similarly prepared from aldehydes or ketones on treatment with 2,2-difluoro-1-iodovinyllithium, generated from 1,1,1-trifluoro-2-iodoethane and lithium diisopropylamide, followed by acetylation. These acetates readily undergo elimination with zinc metal to afford 1,1-difluoroallenes in high yield

NHC-catalyzed generation of difluorocarbene and its application to difluoromethylation of oxygennucleophiles

Controlled generation of difluorocarbene was effected by an NHC catalyst under mild conditions starting from trimethylsilyl 2,2-difluoro-2-fluorosulfonylacetate (TFDA). Cyclohexenones and tetralones were treated with TFDA in the presence of catalytic amounts of N,N′-dimesitylimidazolium chloride and sodium carbonate. The ketones were difluoromethylated with the generated difluorocarbene to afford enol difluoromethyl ethers without difluorocyclopropanation. The ethers thus obtained were dehydrogenated with DDQ to furnish aryl difluoromethyl ethers in high yield. Under similar conditions, secondary amides underwent difluoromethylation selectively on the oxygen atom to give difluoromethyl imidates, which allows the formation of 2-difluoromethoxypyridines

Generation of difluorocarbenes and introduction of fluorinated one carbon units into carbonyl and related compounds

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Preparation of 1,1-Difluoroallenes by Difluorovinylidenation of Carbonyl Compounds

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Synthesis of 2-Difluoroethylated 2H-1,3-Benzoxazines via Proton-Mediated Ring Opening/Interrupted Ritter Reaction of 1,1-Difluorocyclopropanes

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Modular construction of fluoroarenes from a new difluorinated building block via cross-coupling/electrocyclisation/ dehydrofluorination reactions

Palladium-catalysed coupling reactions based on a novel and easy-to-synthesise difluorinated organotrifluoroborate were used to assemble precursors to 6π-electrocyclisations of three different types. Electrocyclisations took place at temperatures between 90 and 240 oC, depending on the central component of the π-system; non-aromatic trienes were most reactive, but even systems which required the temporary dearomatisation of two arenyl sub-units underwent electrocyclisation, albeit at elevated temperatures. Photochemical conditions were effective for these more demanding reactions. The package of methods delivered a structurally-diverse set of fluorinated arenes, spanning a 20 kcal mol-1 range of reactivity, by a flexible route

Synthesis of Ring-Fluorinated Thiophene Derivatives Based on Single C-F Bond Activation of CF3-Cyclopropanes: Sulfanylation and 5-endo-trig Cyclization

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Functionalization of Pyrene To Prepare Luminescent Materials—Typical Examples of Synthetic Methodology

Pyrene-based π-conjugated materials are considered to be an ideal organic electro-luminescence material for application in semiconductor devices, such as organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs) and organic photovoltaics (OPVs), and so forth. However, the great drawback of employing pyrene as an organic luminescence material is the formation of excimer emission, which quenches the efficiency at high concentration or in the solid-state. Thus, in order to obtain highly efficient optical devices, scientists have devoted much effort to tuning the structure of pyrene derivatives in order to realize exploitable properties by employing two strategies, 1) introducing a variety of moieties at the pyrene core, and 2) exploring effective and convenient synthetic strategies to functionalize the pyrene core. Over the past decades, our group has mainly focused on synthetic methodologies for functionalization of the pyrene core; we have found that formylation/acetylation or bromination of pyrene can selectly lead to functionalization at K-region by Lewis acid catalysis. Herein, this Minireview highlights the direct synthetic approaches (such as formylation, bromination, oxidation, and de-tert-butylation reactions, etc.) to functionalize the pyrene in order to advance research on luminescent materials for organic electronic applications. Further, this article demonstrates that the future direction of pyrene chemistry is asymmetric functionalization of pyrene for organic semiconductor applications and highlights some of the classical asymmetric pyrenes, as well as the latest breakthroughs. In addition, the photophysical properties of pyrene-based molecules are briefly reviewed. To give a current overview of the development of pyrene chemistry, the review selectively covers some of the latest reports and concepts from the period covering late 2011 to the present day

Gold-catalyzed electrophilic activation of 1,1-difluoroallenes: α- and γ-selective addition of heteroatom nucleophiles

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