60882-91-9

Upstream product

• 34143-89-0 2,4,6-trimethyl-N-(phenylmethylene)benzenamine 
• 88-05-1 2,4,6-trimethylaniline 
• 100-51-6 benzyl alcohol 
• 100-52-7 benzaldehyde 
• 576-83-0 2,4,6-trimethylphenyl bromide 
• 100-46-9 benzylamine 
• 100-44-7 benzyl chloride 

Downstream Products

• 60882-83-9 N-Benzyl-N-mesityl-2,4,6-trinitrobenzolsulfenamid 
• 71855-59-9 N-Benzyl-N-mesityl-2,4-dinitrobenzolsulfenamid 
• 371773-44-3 benzyl{3-[benzyl(2,4,6-trimethylphenyl)amino]-1H-isoindol-1-ylidene}(2,4,6-trimethylphenyl)ammonium perchlorate 

Relevant academic research and scientific papers

Synthesis of NHC-Iridium(III) Complexes Based on N-Iminoimidazolium Ylides and Their Use for the Amine Alkylation by Borrowing Hydrogen Catalysis

Anionic NHC ligands recently developed in our group, derived from N-iminoimidazolium ylides, were used to synthesize NHC-iridium(III) complexes. Their catalytic activities were evaluated in the amine alkylation of anilines using borrowing hydrogen catalysis. The high-yielding synthesis of a small library of complexes allowed a rapid screening of the ideal steric bulk of the NHC unit and basicity of the anionic tether for the investigated model reaction. A bulky aromatic N group on the imidazolidene moiety is required to achieve high catalytic activity, and the latter is proportional to the basicity of the anionic group. A selected substrate scope of the reaction was performed, providing fair to excellent yields of the desired alkylated anilines.

BF3·Et2O as a metal-free catalyst for direct reductive amination of aldehydes with amines using formic acid as a reductant

A versatile metal- and base-free direct reductive amination of aldehydes with amines using formic acid as a reductant under the catalysis of inexpensive BF3·Et2O has been developed. A wide range of primary and secondary amines and diversely substituted aldehydes are compatible with this transformation, allowing facile access to various secondary and tertiary amines in high yields with wide functional group tolerance. Moreover, the method is convenient for the late-stage functionalization of bioactive compounds and preparation of commercialized drug molecules and biologically relevant N-heterocycles. The procedure has the advantages of simple operation and workup and easy scale-up, and does not require dry conditions, an inert atmosphere or a water scavenger. Mechanistic studies reveal the involvement of imine activation by BF3and hydride transfer from formic acid.

Ru(II) complexes containing (2-(pyren-1-ylmethylene)hydrazinyl)benzothiazole: Synthesis, solid-state structure, computational study and catalysis in N-alkylation reactions

Reactions of (2-(pyren-1-ylmethylene)hydrazinyl)benzothiazole (L) with ruthenium(II) prefabricated precursors [RuHCl(CO)(EPh3)3] and [RuH2(CO)(EPh3)3] (E = P or As) afforded new Ru(II) complexes [RuCl(CO)(EPh3)2(L)] and [RuH(CO)(EPh3)2(L)] (E = P or As) (1–4). All the Ru(II) complexes (1–4) were characterized by IR, NMR spectroscopies, ESI-mass spectrometry and elemental analyses. The solid-state structures of Ru(II) complexes (2 and 3) were established by single crystal X-ray analyses and revealed distorted octahedral geometries around the ruthenium(II) ion and mono anionic bidentate N^N coordination mode for hydrazine ligand. The Ru(II) complexes 2 and 3 were also analyzed using Hirshfeld surface analysis and DFT calculations. Moreover, all the complexes (1–4) were utilized in the N-alkylation reactions of amines using alcohol. Complex 3 was found to be highly active towards N-alkylation of different aromatic amines with alcohol.

Novel N-Substituted Benzomorphan-Based Compounds: From MOR-Agonist/DOR-Antagonist to Biased/Unbiased MOR Agonists

Modifications at the basic nitrogen of the benzomorphan scaffold allowed the development of compounds able to segregate physiological responses downstream of the receptor signaling, opening new possibilities in opioid drug development. Alkylation of the phenyl ring in the N-substituent of the MOR-agonist/DOR-antagonist LP1 resulted in retention of MOR affinity. Moreover, derivatives 7a, 7c, and 7d were biased MOR agonists toward ERK1,2 activity stimulation, whereas derivative 7e was a low potency MOR agonist on adenylate cyclase inhibition. They were further screened in the mouse tail flick test and PGE2-induced hyperalgesia and drug-induced gastrointestinal transit.

Phosphine-Free Well-Defined Mn(I) Complex-Catalyzed Synthesis of Amine, Imine, and 2,3-Dihydro-1 H-perimidine via Hydrogen Autotransfer or Acceptorless Dehydrogenative Coupling of Amine and Alcohol

The application of nontoxic, earth-abundant transition metals in place of costly noble metals is a paramount goal in catalysis and is especially interesting if the air- and moisture-stable ligand scaffold is used. Herein, we report the synthesis of amines/imines directly from alcohol and amines via hydrogen autotransfer or acceptorless dehydrogenation catalyzed by well-defined phosphine-free Mn complexes. Both imines and amines can be obtained from the same set of alcohols and amines using the same catalyst, only by tuning the reaction conditions. The amount and nature of the base are found to be a highly important aspect for the observed selectivity. Both the primary and secondary amines have been employed as substrates for the N-alkylation reaction. As a highlight, we showed the chemoselective synthesis of resveratrol derivatives. Furthermore, the Mn-catalyzed dehydrogenative synthesis of structurally important 2,3-dihydro-1H-perimidines has also been demonstrated. Density functional theory calculations were also carried out to model the reaction path and to calculate the reaction profile.

Potassium Yttrium Ate Complexes: Synergistic Effect Enabled Reversible H2 Activation and Catalytic Hydrogenation

A potassium yttrium benzyl ate complex was generated simply by mixing an yttrium amide and potassium benzyl. The benzyl ate complex could undergo peripheral deprotonation to produce a cyclometalated complex or hydrogenation to give a hydride ate complex. The latter hydride ate complex features a (KH)2 structure protected by two yttrium amide complexes. The synergistic effect between potassium hydride and the amide ligand enables the complex to deprotonate a methyl C-H bond. The combination of intramolecular deprotonation of the hydride ate complex and hydrogenation of the cyclometalated complex constitutes a reversible H2 activation process. Using this process involving formal addition and elimination of H2, we accomplished the catalytic hydrogenation of alkenes, alkynes, and imines.

Well-Defined Amidate-Functionalized N-Heterocyclic Carbene -Supported Rare-Earth Metal Complexes as Catalysts for Efficient Hydroboration of Unactivated Imines and Nitriles

Four amidate-functionalized N-heterocyclic carbene (NHC) rare-earth metal amido complexes [(κ2-N,O-κ1-L)2REN(SiMe3)2] (L = 1-(C6H5CONCH2CH2)-3-(CH3)3C6H2(N(CH)2NC)) [RE = Er (1), Y (2), Dy (3), Gd (4)] were synthesized by one-pot reactions of 2 equiv of (1-(C6H5CONHCH2CH2)-3-(CH3)3C6H2-(N(CH)2NCH))Br (H2LBr) with 5 equiv of KN(SiMe3)3 followed by treatment with 1 equiv of RECl3 in tetrahydrofuran at -40 °C. These complexes were fully characterized, and their catalytic activities toward hydroboration of unactivated imines and nitriles were investigated, and it was found that these complexes displayed excellent activities as well as remarkable functional group compatibility for imine and nitrile substrates such as halo-, alkyl-, hydroxyl-, N,N-dimethylamino-, and nitro- substituents. Among those, the chemoselectivity for this reaction among the common unsaturated functional groups was achieved in the order CO CN > C=N > CO2Et > CC in the current catalytic system, which may facilitate their further application in synthetic chemistry.

Direct Reductive Amination of Carbonyl Compounds Catalyzed by a Moisture Tolerant Tin(IV) Lewis Acid

Despite the ever-broadening applications of main-group ‘frustrated Lewis pair’ (FLP) chemistry to both new and established reactions, their typical intolerance of water, especially at elevated temperatures (>100 °C), represents a key barrier to their mainstream adoption. Herein we report that FLPs based on the Lewis acid iPr3SnOTf are moisture tolerant in the presence of moderately strong nitrogenous bases, even under high temperature regimes, allowing them to operate as simple and effective catalysts for the reductive amination of organic carbonyls, including for challenging bulky amine and carbonyl substrate partners. (Figure presented.).

LiAlH4: From Stoichiometric Reduction to Imine Hydrogenation Catalysis

Imine-to-amine conversion with catalytic instead of stoichiometric quantities of LiAlH4 is demonstrated (85 °C, catalyst loading≥2.5 mol %, pressure≥1 bar). The effects of temperature, pressure, solvent, and catalyst modifications, as well as the substrate scope are discussed. Experimental investigations and preliminary DFT calculations suggest that the catalytically active species is generated in situ: LiAlH4+Ph(H)C=NtBu→LiAlH2[N(tBu)CH2Ph]2. A cooperative mechanism in which Li and Al both play a prominent role is proposed.

Water-Soluble Iridium N-Heterocyclic Carbene Complexes for the Alkylation of Amines with Alcohols

A new series of water-soluble Ir complexes with N-heterocyclic carbene ligands that bear ester and amide groups has been obtained and fully characterized. The new complexes are highly reactive and selective for the alkylation of amines with alcohols with a 1:1 ratio of reactants in water and in the absence of base or other additives. The catalytic system has a broad substrate scope, which allows the synthesis of a variety of primary and secondary amines in excellent yields. A tolerance to a large range of functional groups was obtained.