15429-14-8

Upstream product

• 3886-69-9 (R)-1-phenyl-ethyl-amine 
• 100-44-7 benzyl chloride 
• 618-36-0 rac-methylbenzylamine 
• 100-39-0 benzyl bromide 
• 98-85-1 1-Phenylethanol 
• 103-49-1 dibenzylamine 
• 271-89-6 1-benzofurane 
• 621-07-8 N,N-dibenzylhydroxylamine 
• 100-52-7 benzaldehyde 
• 29601-98-7 N-benzylhydroxylamine hydrochloride 
• 695-84-1 2-allylphenol 
• 100-42-5 styrene 
• 52742-32-2 N,N-dibenzyl-O-benzoylhydroxylamine 
• 136834-99-6 N,N-dibenzyl-O-(4-(trifluoromethyl)benzoyl)hydroxylamine 

Relevant academic research and scientific papers

Facile Synthesis of Chiral Arylamines, Alkylamines and Amides by Enantioselective NiH-Catalyzed Hydroamination

Regio- and enantioselective hydroarylamination, hydroalkylamination and hydroamidation of styrenes have been developed by NiH catalysis with a simple bioxazoline ligand under mild conditions. A wide range of enantioenriched benzylic arylamines, alkylamines and amides can be easily accessed by nitroarenes, hydroxylamines and dioxazolones, respectively as amination reagents. The chiral induction in these reactions is proposed to proceed through an enantiodifferentiating syn-hydronickellation step.

Achieving Aliphatic Amine Addition to Arylalkynes via the Lewis Acid Assisted Triazole-Gold (TA-Au) Catalyst System

Transition metal catalyzed intermolecular hydroamination of the arylalkynes with aliphatic amine is generally problematic due to the good coordination between amine and metal cation. With the combination of 1,2,3-triazole coordinated gold(I) catalyst (TA-Au) and Zn(OTf)2 cocatalyst, this challenging transformation was achieved with good to excellent yields and regioselectivity. Compared to previously reported methods, this approach offered an alternative catalyst system to achieve this fundamental chemical transformation with high efficiency and practical conditions.

Copper-Catalyzed Asymmetric Hydroamination of Styrenes with pivZPhos as Ligand

A copper-catalyzed hydroamination of styrenes using pivZPhos as ligand is reported. Enantioselectivities up to 94% are achieved under optimized conditions with aryl and heteroaryl styrenes. A variety of electrophilic O -benzoylhydroxylamines are well tolerated.

Copper-Catalyzed Ring Opening of Benzofurans and an Enantioselective Hydroamination Cascade

A copper(II) acetate/(R)-DTBM-SEGPHOS-catalyzed ring opening of benzofurans and enantioselective hydroamination cascade with dimethoxymethylsilane (DMMS) and hydroxylamine esters is described. Starting from readily available substituted benzofurans, a series of chiral N,N-dibenzylaminophenols, which are of high interest in pharmaceutical chemistry, were obtained with excellent enantioselectivities (up to 66 % yield, 94 % ee).

A Practical Electrophilic Nitrogen Source for the Synthesis of Chiral Primary Amines by Copper-Catalyzed Hydroamination

A mild and practical method for the catalytic installation of the amino group across alkenes and alkynes has long been recognized as a significant challenge in synthetic chemistry. As the direct hydroamination of olefins using ammonia requires harsh conditions, the development of suitable electrophilic aminating reagents for formal hydroamination methods is of importance. Herein, we describe the use of 1,2-benzisoxazole as a practical electrophilic primary amine source. Using this heterocycle as a new amino group delivery agent, a mild and general protocol for the copper-hydride-catalyzed hydroamination of alkenes and alkynes to form primary amines was developed. This method provides access to a broad range of chiral α-branched primary amines and linear primary amines, as demonstrated by the efficient synthesis of the antiretroviral drug maraviroc and the formal synthesis of several other pharmaceutical agents.

Mechanistic Studies Lead to Dramatically Improved Reaction Conditions for the Cu-Catalyzed Asymmetric Hydroamination of Olefins

Enantioselective copper(I) hydride (CuH)-catalyzed hydroamination has undergone significant development over the past several years. To gain a general understanding of the factors governing these reactions, kinetic and spectroscopic studies were performed on the CuH-catalyzed hydroamination of styrene. Reaction profile analysis, rate order assessment, and Hammett studies indicate that the turnover-limiting step is regeneration of the CuH catalyst by reaction with a silane, with a phosphine-ligated copper(I) benzoate as the catalyst resting state. Spectroscopic, electrospray ionization mass spectrometry, and nonlinear effect studies are consistent with a monomeric active catalyst. With this insight, targeted reagent optimization led to the development of an optimized protocol with an operationally simple setup (ligated copper(II) precatalyst, open to air) and short reaction times (30 min). This improved protocol is amenable to a diverse range of alkene and alkyne substrate classes.

Enantio- and regioselective CuH-catalyzed hydroamination of alkenes

A highly enantio- and regioselective copper-catalyzed hydroamination reaction of alkenes has been developed using diethoxymethylsilane and esters of hydroxylamines. The process tolerates a wide variety of substituted styrenes, including trans-, cis-, and β,β-disubstituted styrenes, to yield α-branched amines. In addition, aliphatic alkenes coupled to generate exclusively the anti-Markovnikov hydroamination products.

Copper-catalyzed intermolecular regioselective hydroamination of styrenes with polymethylhydrosiloxane and hydroxylamines

Playing Reversi with H and N: A copper-catalyzed intermolecular regioselective hydroamination of styrenes with polymethylhydrosiloxane and hydroxylamine derivatives has been developed. The catalysis accommodates challenging β-substituted substrates. Moreover, the chiral biphosphine-ligated copper complex successfully forms benzylamines with good enantiomeric ratios. Copyright

Salt-free synthesis of tertiary amines by ruthenium-catalyzed amination of alcohols

The amination of secondary alcohols to give tertiary amines in the presence of different in situ generated ruthenium catalysts has been investigated in detail. By applying a combination of [Ru3(CO)12] and N-phenyl-2-(dicyclohexylphosphanyl) pyrrole as the catalyst, cyclic amines can be alkylated with different alcohols in high yield, whereas aliphatic amines gave transalkylation side products. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

Cesium effect: High chemoselectivity in direct N-alkylation of amines

A novel method for the mono-N-alkylation of primary amines, diamines, and polyamines was developed using cesium bases in order to prepare secondary amines efficiently. A cesium base not only promoted alkylation of primary amines but also suppressed overalkylations of the produced secondary amines. Various amines, alkyl bromides, and alkyl sulfonates were examined, and the results demonstrated this methodology was highly chemoselective to favor mono-N-alkylation over dialkylation. In particular, use of either sterically demanding substrates or amino acid derivatives afforded the secondary amines exclusively, offering wide applications in peptidomimetic syntheses.