The selective introduction of fluorine atom(s) and fluorinated moieties into organic molecules has become an important fast-growing research field, since atoms play crucial roles in life science materials science-related applications. Similar to the trifluoromethyl group, both difluoromethyl monofluoromethyl groups can often bring about many beneficial effects target molecules, a variety CF(2)H- CH(2)F-containing pharmaceuticals agrochemicals have been developed. Among synthetic methods for...

Efficient fluoroalkylations have been proven to be a highly useful strategy for the synthesis of bioactive fluorine-containing compounds and other materials. The design use single category reagents multiple synthetic goals are much more attractive preparative organic chemists. In this Account, we show how succeeded in nucleophilic trifluoromethylation, difluoromethylation, difluoromethylenation, (phenylsulfonyl)difluoromethylation, (phenylthio)difluoromethylation, monofluoromethylation as...

The radical fluoroalkylation of isocyanides with fluorinated sulfones is enabled by visible-light photoredox catalysis. A wide range readily available mono-, di-, and trifluoromethyl heteroaryl can thus be used as efficient reagents under mild conditions. This method not only describes a new synthetic application sulfones, but also provides route to fluoroalkyl radicals.

Highly versatile: The Ruppert–Prakash reagent (Me3SiCF3) can be an efficient source of difluorocarbene. By varying the nonmetallic initiator that is used (F− at lower temperatures and I− higher temperatures), a range structurally diverse alkenes alkynes converted into corresponding gem-difluorinated cyclopropanes cyclopropenes in good yields (see scheme). Detailed facts importance to specialist readers are published as ”Supporting Information”. Such documents peer-reviewed, but not...

Two-in-one: Me3 SiCF2 Br is an efficient difluorocarbene source and compatible with both neutral aqueous basic conditions. Bromide-ion-initiated [2+1] cycloaddition alkenes/alkynes hydroxide ion promoted α-addition (thio)phenols, (thio)alcohols, sulfinates, heterocyclic amines, H-phosphine oxides give the corresponding gem-difluorinated compounds broad functional-group tolerance.

Difluorocarbene is a versatile, reactive intermediate for use in organic synthesis. Over the past decade, significant progress has been made difluorocarbene chemistry owing to increasing demand various fluorinated molecules. Not only substrate scope some classical reagents largely expanded, but also new and environmentally friendly difluoromethylation <i>gem</i>-difluorocyclization have developed. This review summarizes difluoromethylation, <i>gem</i>-difluorocyclopropanation,...

Abstract Owing to the excellent performance of fluorinated compounds in areas pharmaceuticals, agrochemicals, and materials chemistry, organic chemists have made great efforts towards selective incorporation fluorine or moieties into molecules through nucleophilic, electrophilic, radical, metal‐catalyzed pathways. Impressive progress fluorination perfluoroalkylation (especially trifluoromethylation) reactions has been over past few decades. However, methods for incorporating lightly groups...

A new olefination protocol for transition-metal-free cross-coupling of two carbene fragments arising from different sources, namely, a nonfluorinated fragment resulting diazo compound and difluorocarbene derived Ruppert–Prakash reagent (TMSCF3) or TMSCF2Br, has been developed. This gem-difluoroolefination proceeds through the direct nucleophilic addition compounds to followed by elimination N2. Compared previously reported Cu-catalyzed with TMSCF3, which possesses narrow substrate scope due...

Dual action: The Lewis acid CuF2⋅2 H2O efficiently catalyzes the reaction between electrophilic fluoroalkylating agents and α,β-unsaturated carboxylic acids by dually activating both reactants, thus affording di- trifluoromethyl alkenes in high yields with excellent E/Z selectivity. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents peer-reviewed, but not copy-edited or typeset. They made available submitted authors. Please note:...

A novel Cu-catalyzed gem-difluoroolefination of diazo compounds is described. This transformation starts from readily available TMSCF3 and compounds, via trifluoromethylation followed by C–F bond cleavage, to afford the desired 1,1-difluoroalkene products.

Fluorinated sulfinate salts RfSO2Na (Rf = CF2H, CF2Ph, and CH2F) have been prepared via NaBH4-mediated reduction of the corresponding benzo[d]thiazol-2-yl sulfones, their synthetic application as di- monofluoroalkyl radical precursors is demonstrated in silver-catalyzed cascade fluoroalkylation/aryl migration/SO2 extrusion conjugated N-arylsulfonylated amides.

We report the first iron-catalyzed difluoromethylation of arylzincs with difluoromethyl 2-pyridyl sulfone via selective C–S bond cleavage. This method employs readily available, bench-stable fluoroalkyl reagent and inexpensive iron catalyst, allowing facile access to structurally diverse difluoromethylated arenes at low temperatures. The experiment employing a radical clock indicates involvement species in this process.

ConspectusAs fluorine has played an increasingly important role in modulating the physical, chemical, and biological properties of organic molecules, selective introduction atom(s) or fluorinated moieties into target molecules become a powerful tool development new pharmaceuticals, agrochemicals, functional materials. In this context, difluoromethylene (CF2) difluoromethyl (CF2H) groups are special interest because their ability to serve as bioisosteres ethereal oxygen atoms hydroxyl (OH)...

The first alpha-difluoromethyl sulfoximine compound, 2, was successfully prepared by using the copper(II)-catalyzed nitrene transfer reaction. Compound 2 found to be a novel and efficient difluoromethylation reagent for transferring CF(2)H group S-, N-, C-nucleophiles. Deuterium-labeling experiments suggest that difluorocarbene mechanism is involved in current reactions.

The degradation mechanism of sulfonated poly(ether ether ketone) membranes under VFB operating conditions was clarified, which is highly beneficial for improving the chemical stability hydrocarbon ion exchange membranes.

Copper-mediated trifluoromethylation of α-diazo esters with TMSCF3 reagent has been developed as a new method to prepare α-trifluoromethyl esters. This reaction represents the first example fluoroalkylation non-fluorinated carbene precursor. Water plays an important role in promoting by activating “CuCF3” species prepared from CuI/TMSCF3/CsF (1.0:1.1:1.1). The scope this is broad, and its efficiency demonstrated synthesis variety aryl-, benzyl-, alkyl-substituted 3,3,3-trifluoropropanoates.

An unprecedented silver-mediated vicinal trifluoromethylation–iodination of arynes that quickly introduces CF3 and I groups onto aromatic rings in a single step to give o-trifluoromethyl iodoarenes has been developed. A new reactivity AgCF3 revealed, 2,2,6,6-tetramethylpiperidine plays an important role this difunctionalization reaction.

Abstract The new millennium has witnessed the rapid development of synthetic organofluorine chemistry all over world, and chemists in China have made significant contributions this field. This review aims to provide a brief introduction China's primary innovations from 2000 early 2017, covering fluorination, fluoroalkylation, fluoromethylthiolation, fluoroolefination polyfluoroarylation, as well synthesis with fluorinated building blocks. Recent advances difluorocarbene carbon–fluorine bond...

A chloride ion-catalyzed generation of difluorocarbene from a relatively non-toxic and inexpensive precursor, Me(3)SiCF(2)Cl (1), under mild neutral conditions leads to an efficient preparation gem-difluorocyclopropenes difluorocyclopropanes through [2 + 1] cycloaddition reactions with alkynes alkenes, respectively.

We have successfully accomplished the nucleophilic fluoroalkylation of α,β-enones, arynes, and activated alkynes with fluorinated sulfones. It was found that for acylic although reaction medium structure enones can all influence regioselectivity alkylation reactions, hard/soft nature carbanions played a major role. By using 1,4- 1,2-addition product ratio as probe to determine above-mentioned four halogenated carbanions, order softness these be given follows: [(PhSO2)2CF−] (20) ≈ PhSO2CCl2−...

Since 1995, Me3SiCF2H has been widely believed to be an inefficient difluoromethylating agent, which requires harsh reaction conditions cleave its rather inert Si–CF2H bond. However, it now found that, by using a proper Lewis base activator, can efficiently difluoromethylate various aldehydes, ketones, and imines give the corresponding products in good excellent yields at room temperature or even −78 °C.