64999-34-4

Upstream product

• 2051-90-3 Dichlorodiphenylmethane 
• 618-36-0 rac-methylbenzylamine 
• 908093-98-1 diazodiphenylmethane 
• 7699-79-8 benzhydrylidene-benzyl-amine 
• 77-78-1 dimethyl sulfate 
• 1013-88-3 Benzophenone imine 
• 100-41-4 ethylbenzene 
• 98-86-2 acetophenone 
• 574-66-3 Benzophenone oxime 
• 3362-33-2 diphenylmethanone O-benzoyl oxime 
• 5267-34-5 aminodiphenylmethane hydrochloride 
• 91-00-9 Benzhydrylamine 
• 119-61-9 benzophenone 
• 29412-58-6 N-(diphenylmethyl)-1-phenylethan-1-imine 

Downstream Products

• 59320-64-8 (R)-3,3-Diphenyl-2-((R)-1-phenyl-ethyl)-oxaziridine 
• 59320-64-8 (R)-3,3-Diphenyl-2-((S)-1-phenyl-ethyl)-oxaziridine 
• 618-36-0 rac-methylbenzylamine 
• 133469-21-3 N-benzhydryl-1-phenylethan-1-amine 
• 29412-58-6 N-(diphenylmethyl)-1-phenylethan-1-imine 

Relevant academic research and scientific papers

One-Pot Synthesis of Primary and Secondary Aliphatic Amines via Mild and Selective sp3 C?H Imination

The direct replacement of sp3 C?H bonds with simple amine units (?NH2) remains synthetically challenging, although primary aliphatic amines are ubiquitous in medicinal chemistry and natural product synthesis. We report a mild and selective protocol for preparing primary and secondary aliphatic amines in a single pot, based on intermolecular sp3 C?H imination. The first C?H imination of diverse alkanes, this method shows useful site-selectivity within substrates bearing multiple sp3 C?H bonds. Furthermore, this reaction tolerates polar functional groups relevant for complex molecule synthesis, highlighted in the synthesis of amine pharmaceuticals and amination of natural products. We characterize a unique C?H imination mechanism based on radical rebound to an iminyl radical, supported by kinetic isotope effects, stereoablation, resubmission, and computational modeling. This work constitutes a selective method for complex amine synthesis and a new mechanistic platform for C?H amination.

Selective Hydrogen Transfer in N-(Diphenylmethyl)-1-phenylethan-1-imine

Abstract: Proton transfer processes mediate many organic reactions. How to realizestereochemical control of this process has always been a challenging topic inthe field of asymmetric catalysis. In this study, N-(diphenyl-methyl)-1-phenylethan-1-imine (Schiff base derivedfrom 2,2-diphenylethan-1-amine and acetophenone) was used as substrate, anddifferent near neutral solvents and various chiral metal complex catalysts wereused to carry out photoinduced C=N double bond transfer in the substrate underirradiation with a mercury ultraviolet lamp. The double bond transfer in thesubstrate molecule was highly selective. Solvents containing strongelectronegative atoms like oxygen and chlorine, such as alcohols, aldehydes, andcarbon tetrachloride, were more effective than other solvents under high lightintensity. The 1,3-proton transfer process involves photo-excitation of theSchiff base and coordination of the latter to the central metal atom of thechiral catalyst, so that the substrate molecule is placed in a stable chiralenvironment to form a transition state. The strongly electro-negative atom ofthe near-neutral solvent attracts the active α-hydrogen from the excited Schiffbase molecule to form a negatively charged delocalized π-bond structure. Thesubsequent proton addition yields more stable molec-ular structure to completethe selective proton transfer process. Among the examined chiral catalysts,divalent tin porphyrin was the most effective, and the product yield andenantiomeric excess were 98% and 91.49%, respectively. The describedphotoinduced C=N double bond transfer in N-(diphenylmethyl)-1-phenyl-ethan-1-imine is characterized by mildconditions (room temperature), high stereoselectivity, and simpleoperation.

Direct C(sp3)-N Radical Coupling: Photocatalytic C-H Functionalization by Unconventional Intermolecular Hydrogen Atom Transfer to Aryl Radical

An unconventional approach for intermolecular direct C(sp3)-N radical coupling has been developed by photocatalytic C(sp3)-H activation of simple alkyl substrates using O-benzoyl oximes. The selective photocatalytic energy-transfer-driven homolysis followed by decarboxylation generates the persistent iminyl radical and aryl radical, which would undergo an unprecedented intermolecular hydrogen atom abstraction from the alkyl substrate to provide the key C(sp3) radical. Selective radical-radical C-N cross-coupling furnishes imines which are valuable amine building blocks.

Synthesis of α-Substituted Primary Benzylamines through Copper-Catalyzed Cross-Dehydrogenative Coupling

A copper-catalyzed route to α-substituted, primary benzylamines by C-H functionalization of alkylarenes is described. The method directly affords the amine hydrochloride salt. Catalyst loadings down to 0.1 mol % in combination with scalability, insensitivity to air and moisture, and no need for column chromatography makes the procedure highly practical. The facile synthesis of the racemate of a blockbuster drug highlights the relevance for the development of pharmaceuticals. Preliminary mechanistic data are also included.

Benzhydrylamine: An effective aminating agent for the synthesis of primary amines

Aldehydes, ketones, alkyl toluene-p-sulfonates and halides are converted into the corresponding primary amines with benzhydrylamine as a valuable ammonia synthon in moderate to excellent yields.

Cyclopalladated benzophenone imines: Synthesis, antitumor activity, cell accumulation, dna interaction, and cathepsin b inhibition

The synthesis of the endo five-membered cyclo-ortho-palladated benzophenone imines [Pd{C6H4(Ph)C=NR}]2(μ-X)2 [1 (X = OAc), 2 (X = Cl), a (R = phenyl), b (R = 1-naphthyl), c (R = benzyl), d (R = α-methylbenzyl)], and trans-N,P-[Pd{C6H4(Ph)C=NR}X(PPh3)] [3 (X = OAc), 4 (X = Cl), a (R = phenyl), b (R = 1-naphthyl), c (R = benzyl), d (R = α-methylbenzyl)] and the X-ray molecular structure of 1a, 1c, 1d, 4a, 4b, and 4c are reported. The antitumor activity, DNA interaction, and cathepsin B inhibition of palladium compounds a-d were studied and compared with those previously reported for palladium compounds e with R = H and compound 4f analogous to 4e but with a platinum(II) center. The IC50 values against a panel of human cancer cell lines allowed the establishment of a qualitative relationship between their structure and antitumor activity. Compounds 3e, 4e, and 4f were the most active ones in relation to their in vitro anticancer activity. Compounds 3e and 4e were about 4 times more active than cisplatin against the MDA-MB-231 and MCF-7 breast human cancer lines, and compound 4f was about 4 times more active than cisplatin against the cisplatin-resistant HCT-116 colon human cancer cell line. In addition, compound 3e was 3 times less cytotoxic than cisplatin toward the quiescent HUVEC cells. Accumulation of palladium compounds e and b in the MDA-MB-231 cell line was considerably greater than that of cisplatin in the same cell line, but palladium compounds b were noncytotoxic. Some of these complexes altered the DNA tertiary structure in a similar way to cisplatin but at higher concentration, and most cytotoxic ones did not present a high efficiency as cathepsin B inhibitors.

Revisiting optically active quaternary derivatives made from prolinol as phase transfer catalysts

New non-racemic ammonium salts derived from prolinol have been prepared which are stereogenic both at N and at C. Absolute configurations rest on X- ray structures for 3c and 7a. The new compounds have been tested in a number of known enantioselective phase transfer catalytic (PTC) reactions to gain insight into steric control factors in such processes. Only very moderate e.e.s were observed. A SAMP hydrazone related catalyst (7a) reported by other authors was fully characterized. Racemic reaction products were obtained in two alkylations of diphenylmethylene benzylimine in the presence of this pure catalyst 7a. Very high e.e.s reported previously by others could not be reproduced.

Bis(acetylacetonato)copper(II) Catalysed Reaction of Diphenyldiazomethane with Primary Amines

The titel reaction using (+/-)-α-phenylethylamine, benzhydrylamine and (+/-)-α-p-tolylethylamine as primary amines leads to the formation of benzophenone N-substituted imines (IVa-c).The insertion of diphenylcarbene, formed from the decomposition of diphe