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• 110-89-4 piperidine 
• 352-11-4 1-chloromethyl-4-fluorobenzene 
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• 459-56-3 4-fluorobenzylic alcohol 
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• 459-46-1 4-Fluorobenzyl bromide 

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• 275815-51-5 1,3-Dihydro-4'-[4-fluorophenylmethyl]-4-nitro-spiro[2H-isoindole-2,1'-piperidinium] bromide 
• 459-57-4 4-fluorobenzaldehyde 
• 58547-67-4 N-(p-fluorobenzoyl)piperidine 

Relevant academic research and scientific papers

Manganese-Catalyzed Hydroborations with Broad Scope

Reductive transformations of easily available oxidized matter are at the heart of synthetic manipulation and chemical valorization. The applications of catalytic hydrofunctionalization benefit from the use of liquid reducing agents and operationally facile setups. Metal-catalyzed hydroborations provide a highly prolific platform for reductive valorizations of stable C=X electrophiles. Here, we report an especially facile, broad-scope reduction of various functions including carbonyls, carboxylates, pyridines, carbodiimides, and carbonates under very mild conditions with the inexpensive pre-catalyst Mn(hmds)2. The reaction could be successfully applied to depolymerizations.

Iodine-Mediated Coupling of Cyclic Amines with Sulfonyl Hydrazides: an Efficient Synthesis of Vinyl Sulfone Derivatives

An efficient iodine-mediated coupling of cyclic amines with sulfonyl hydrazides is reported. This transformation opens a new route to the synthesis of vinyl sulfones derivatives, which is a common structural motif in natural products and pharmaceuticals. Tentative mechanistic studies suggest that this reaction is likely to involve a radical process.

La[N(sime3)2]3-catalyzed deoxygenative reduction of amides with pinacolborane. scope and mechanism

Tris[N,N-bis(trimethylsilyl)amide]lanthanum (LaNTMS) is an efficient and selective homogeneous catalyst for the deoxygenative reduction of tertiary and secondary amides with pinacolborane (HBpin) at mild temperatures (25-60 °C). The reaction, which yields amines and O(Bpin)2, tolerates nitro, halide, and amino functional groups well, and this amide reduction is completely selective, with the exclusion of both competing inter- and intramolecular alkene/alkyne hydroboration. Kinetic studies indicate that amide reduction obeys an unusual mixed-order rate law which is proposed to originate from saturation of the catalyst complex with HBpin. Kinetic and thermodynamic studies, isotopic labeling, and DFT calculations using energetic span analysis suggest the role of a [(Me3Si)2N]2La-OCHR(NR′2)[HBpin] active catalyst, and hydride transfer is proposed to be ligand-centered. These results add to the growing list of transformations that commercially available LaNTMS is competent to catalyze, further underscoring the value and versatility of lanthanide complexes in homogeneous catalysis.

Derisking the Cu-Mediated 18F-Fluorination of Heterocyclic Positron Emission Tomography Radioligands

Molecules labeled with fluorine-18 (18F) are used in positron emission tomography to visualize, characterize and measure biological processes in the body. Despite recent advances in the incorporation of 18F onto arenes, the development of general and efficient approaches to label radioligands necessary for drug discovery programs remains a significant task. This full account describes a derisking approach toward the radiosynthesis of heterocyclic positron emission tomography (PET) radioligands using the copper-mediated 18F-fluorination of aryl boron reagents with 18F-fluoride as a model reaction. This approach is based on a study examining how the presence of heterocycles commonly used in drug development affects the efficiency of 18F-fluorination for a representative aryl boron reagent, and on the labeling of more than 50 (hetero)aryl boronic esters. This set of data allows for the application of this derisking strategy to the successful radiosynthesis of seven structurally complex pharmaceutically relevant heterocycle-containing molecules.

Mild and selective Et2Zn-catalyzed reduction of tertiary amides under Hydrosilylation conditions

Diethylzinc (Et2Zn) can be used as an efficient and chemoselective catalyst for the reduction of tertiary amides under mild reaction conditions employing cost-effective polymeric silane (PMHS) as the hydride source. Crucial for the catalytic activity was the addition of a substoichiometric amount of lithium chloride to the reaction mixture. A series of amides containing different additional functional groups were reduced to their corresponding amines, and the products were isolated in good-to-excellent yields.

Reusable supported ruthenium catalysts for the alkylation of amines by using primary alcohols

Efficient and recyclable ruthenium catalysts were synthesized from readily available polystyrene-or silica-supported phosphine ligands. Catalysts bound to the polymer support through an ether linkage showed good to excellent activity towards the N-alkylation of primary and secondary amines to afford the alkylated products in 62-99 % yield at 120-140°C. The supported phosphine ligand/ruthenium ratio was found to be crucial for higher catalytic activity and lower ruthenium leaching. The continuous flow N-alkylation of amines was demonstrated by using the supported catalyst in a column reactor. By adopting the hydrogen-borrowing strategy, the synthesis of the anti-Parkinson agent Piribedil was established in 98 % yield at 140°C. Support group steals the show: An efficient Ru-based heterogeneous catalyst from readily available supported phosphine ligands is developed. The nature of the linkage and the extent of ruthenium incorporation are crucial in determining the catalytic activity. The catalyst can be recycled and used under continuous flow in a packed-bed reactor. The alkylation of cyclic amines is achieved in excellent yield at moderate temperatures in the absence of any external base.

Base-promoted N-alkylation using formamides as the N-sources in neat water

An efficient catalyst-free, alternative method for the C-N bond formation reaction of alkyl electrophiles using formamides as the N-sources was achieved under mild conditions. The reaction possesses the advantages of a broad range of substrates scope and wide functional group tolerance. It should also be noted that this process was performed using the environmentally benign water as the sole solvent, and high yield can also be achieved in ten-gram scale.

Highly efficient amination in neat water of benzyl chlorides with dialkylformamides catalysed by N-heterocyclic carbene-palladium(II)-1- methylimidazole complex

Dialkylformamides are excellent N-sources in the amination of benzyl chlorides when catalysed by a NHC-Pd(II)-Im complex. In the presence of NaOH and the catalyst, variously substituted benzyl chlorides and five different dialkylformamides reacted smoothly to afford the corresponding N,N-dialkyl-benzylamines in good to almost quantitative yields in eco-friendly solvent water at 50 °C within 3 h.

Direct hydrosilylation of tertiary amides to amines by an in situ formed iron/N-heterocyclic carbene catalyst

Tertiary amides were efficiently reduced to their corresponding tertiary amines in high isolated yields by using the commercially available and inexpensive polymeric silane polymethylhydrosiloxane (PMHS) as the reducing agent. The reaction is efficiently catalyzed by an in situ generated iron/N-heterocyclic carbene complex (1 mol-%) obtained from iron(II) acetate and 1-(2-hydroxy-2-phenylethyl)-3-methylimidazolium triflate ([PhHEMIM][OTF]). A catalytic amount of lithium chloride (1 mol-%) present in the reaction mixture significantly reduced the reaction time and increased the chemoselectivity of the reduction process. Tertiary amides are reduced to their corresponding tertiary amines in high isolated yields by using the polymeric silane polymethylhydrosiloxane (PMHS) in the presence of an in situ generated iron/N-heterocyclic carbene complex (1 mol-%), generated from iron(II) acetate and 1-(2-hydroxy-2-phenylethyl)-3-methylimidazolium triflate ([PhHEMIM][OTF]), and a catalytic amount of lithium chloride (1 mol-%). Copyright

Zinc-catalyzed chemoselective reduction of tertiary and secondary amides to amines

General and convenient procedures for the catalytic hydrosilylation of secondary and tertiary amides under mild conditions have been developed. In the presence of inexpensive zinc catalysts, tertiary amides are easily reduced by applying monosilanes. Key to success for the reduction of the secondary amides is the use of zinc triflate and disilanes with dual Si-H moieties. The presented hydrosilylations proceed with excellent chemoselectivity in the presence of sensitive ester, nitro, azo, nitrile, olefins, and other functional groups, thus making the method attractive for organic synthesis.