Difluoroalkylated compounds play a remarkably important role in life and materials sciences because of the unique characteristics difluoromethylene (CF2) group. In particular, precise introduction CF2 group at benzylic position can dramatically improve biological properties corresponding molecules. As consequence, difluoroalkylation aromatic has become powerful strategy modulating bioactivities organic However, efficient strategies to selectively synthesize difluoroalkylated arenes had been...

Abstract The palladium‐catalyzed difluoroalkylation of aryl boronic acids with bromodifluoromethylphosphonate, bromodifluoroacetate, and further derivatives has been developed. This method provides a facile useful access to series functionalized difluoromethylated arenes (ArCF 2 PO(OEt) , ArCF CO Et, CONR 1 R ) that have important applications in drug discovery development. Preliminary mechanistic studies reveal single electron transfer (SET) pathway may be involved the catalytic cycle.

Abstract An efficient palladium‐catalyzed Heck‐type reaction of fluoroalkyl halides, including perfluoroalkyl bromides, trifluoromethyl iodides, and difluoroalkyl has been developed. The proceeds under mild conditions with high efficiency broad substrate scope, provides a general straightforward access to fluoroalkylated alkenes which are interest in life material sciences.

An unprecedented example of Pd-catalyzed difluoromethylation aryl boronic acids with bromodifluoroacetate is described. The reaction proceeds under mild conditions hydroquinone and Fe(acac)3 as additives. Preliminary mechanistic studies reveal that a difluorocarbene pathway involved in the reaction, which unusual compared to most traditional approaches. This has advantages high efficiency excellent functional group compatibility, even toward bromide hydroxy group, thus providing useful...

The H8-BINOL-derived, phosphoric acid catalyzed, highly enatioselective alkylation reaction of enamides with indolyl alcohols has been described. A derived from H8-BINOL enabled an asymmetric alpha-alkylation to give beta-aryl 3-(3-indolyl)propanones in high yields (up 96%) and excellent enantioselectivity 96% ee).

A first example of Pd-catalyzed gem-difluoroallylation organoborons using 3-bromo-3,3-difluoropropene (BDFP) in high efficiency with α/γ-substitution regioselectivity has been developed. The reaction can also be extended to substituted BDFPs and advantages low catalyst loading (0.8 0.01 mol %), broad substrate scope, excellent functional group compatibility, thus providing a facile route for practical application drug discovery development.

A copper-catalyzed cross-coupling of iodobenzoates with bromozinc-difluorophosphonate, generated from diethyl bromodifluoromethylphosphonate and zinc in dioxane, is reported. The notable features this reaction are its high efficiency, excellent functional group compatibility, operational simplicity. This protocol provides a useful facile access to aryldifluorophosphonates interest life science.

A metal-free oxidative coupling of methyl ketones and primary or secondary amines to α-ketoamides has been developed. Four intermediates, α-iodoketone, α-aminoketone, iminium intermediate, α-hydroxy amine have identified through a series control experiments. The atom-economic methodology can be scaled-up, tolerates variety functional groups, is operationally simple.

Abstract The palladium‐catalyzed difluoroalkylation of aryl boronic acids with bromodifluoromethylphosphonate, bromodifluoroacetate, and further derivatives has been developed. This method provides a facile useful access to series functionalized difluoromethylated arenes (ArCF 2 PO(OEt) , ArCF CO Et, CONR 1 R ) that have important applications in drug discovery development. Preliminary mechanistic studies reveal single electron transfer (SET) pathway may be involved the catalytic cycle.

The first example of intermolecular regioselective α-arylation heteroatom-substituted enones with polyfluoroarenes via twofold C–H bond functionalization using a palladium catalyst is reported. This approach provides rapid access to wide range α-fluoroarylated interest in life science.

Abstract An efficient palladium‐catalyzed Heck‐type reaction of fluoroalkyl halides, including perfluoroalkyl bromides, trifluoromethyl iodides, and difluoroalkyl has been developed. The proceeds under mild conditions with high efficiency broad substrate scope, provides a general straightforward access to fluoroalkylated alkenes which are interest in life material sciences.

A mild and efficient nickel-catalyzed reductive cross-coupling between fluorinated secondary alkyl bromides (hetero)aryl iodides is described. The use of FeBr2 as an additive successfully overcomes the hydrodebromination β-fluorine elimination substrates allows synthesis a wide range trifluoromethyl difluoroalkyl containing aliphatic compounds with fluoroalkyl substituted tertiary carbon center. notable features this protocol are synthetic operational simplicity without preparation moisture...

An efficient method for the synthesis of difluoroalkylated alkenes through palladium-catalyzed Heck-type reaction with functionalized difluoromethyl bromides has been developed. The advantages this protocol are its synthetic simplicity, excellent functional group compatibility, and late-stage difluoroalkylation biologically relevant molecules, thus paving a new way application in drug discovery development. Mechanistic studies revealed that free difluoroalkyl radicals, initiated by...

The first iron-catalyzed defluorosilylation of unactivated gem-difluoroalkenes was developed, delivering gem-disilylated alkenes and (E)-silylated with excellent efficiency. This protocol features good functional group compatibility regio- stereoselectivity, enabling the late-stage silylation biologically relevant compounds, thus providing opportunities for applications in medicinal chemistry. Preliminary mechanistic studies DFT calculations reveal that a nucleophilic addition elimination...

Transition-metal-catalyzed reductive cross-coupling reactions have been developed as one of the important tools for constructing C–C bonds. These involve direct coupling two distinct electrophiles promoted by transition metals and reductants. Notably, these methods offer advantages over conventional because they circumvent need air- moisture-sensitive organometallic reagents while being simple to operate exhibiting good compatibility with various functional groups. In recent years, diboron...

The bis(NHC) (NHC = N-heterocyclic carbene)-based CNC-pincer rare-earth-metal amido complexes LRE[N(SiMe3)2]2 (L 4-CH3-2-{R-[N(CH)2CN]}C6H3]2N; L2, R CH3; L3, CH(CH3)2) were synthesized and characterized, their catalytic activities toward hydrophosphination of heterocumulenes developed. Reactions bis[2-(3-methylimidazolium)-4-methylphenyl]amine diiodide (H3L2I2) or bis[2-(3-isopropylimidazolium)-4-methylphenyl]amine (H3L3I2) with 5 equiv NaN(SiMe3)2 followed by treatment 1 RECl3 in THF at...

Abstract A three‐component synthesis of 2‐substituted benzothiazoles from aryl amines, elemental sulfur and styrenes or acetylenes in 1‐methylpyrrolidin‐2‐one (NMP) is described. Two C−S one C−N bonds were selectively formed one‐pot under metal‐free conditions. magnified image

The first example of the thiyl radical promoted ligand-free iron-catalyzed oxidative cleavage alkenes using molecular oxygen (1 atm) has been developed.