14429-17-5

Upstream product

• 100-46-9 benzylamine 
• 100-06-1 1-(4-methoxyphenyl)ethanone 

Downstream Products

• 15043-47-7 [Rh(bis(diphenyl)phosphinoethane)₂][Cl] 
• 850199-99-4 [N,o-C-(p-methoxy-phenylmethylbenzylaminato)]hydrido(acetone)bis(triphenylphosphine)rhodium(III) hexafluorophosphate 
• 14429-03-9 N-benzyl-N-(α-methyl-p-methoxybenzyl)amine 

Relevant academic research and scientific papers

Base-Catalyzed [3 + 2] Cycloaddition of N-Benzyl Ketimines to Arylacetylenes Followed by Oxidation: A One-Pot Access to Polyarylated 2 H-Pyrroles via Intermediate Pyrrolines

N-Benzyl ketimines undergo [3 + 2] cycloaddition with arylacetylenes in the KOBut/DMSO solution to 2,3,5-triarylpyrrolines, which are oxidized (chloranil, DDQ) in situ to 2,3,5-triaryl-2H-pyrroles in 53-71% yields. The intermediate 1-pyrrolines can be isolated in 31-91% yields and separately oxidized to the corresponding 2H-pyrroles.

Hydroboration Catalyzed by 1,2,4,3-Triazaphospholenes

The synthesis and study of the catalytic activity of 1,2,4,3-triazaphospholenes (TAPs) is reported. TAPs represent a more modular scaffold than previously reported diazaphospholenes. TAP halides were shown to catalyze the 1,2 hydroboration of 19 imines, and three α,β unsaturated aldehydes with pinacolborane, including examples that did not undergo hydroboration by previously reported diazaphospholene systems. DFT calculations support a mechanism where a triazaphospholene cation interacts with the substrate, a mechanism distinct from diazaphospholene catalyzed hydroborations.

Asymmetric Imine Hydroboration Catalyzed by Chiral Diazaphospholenes

The first use of diazaphospholenes as chiral catalysts has been demonstrated with enantioselective imine hydroboration. A chiral diazaphospholene prepared in a simple three-step synthesis from commercial materials has been shown to achieve the highest enantioselectivity for the hydroboration of alkyl imines with pinacolborane reported to date. Enantiomer ratios of up to 88:12 were obtained with low (2 mol %) catalyst loadings. Twenty examples of asymmetric reduction employing this main-group catalysis protocol, including the synthesis of the pharmaceuticals ent-rasagiline and fendiline, are shown.

Metal-free oxidative cross-coupling of diazirines with arylboronic acids

We report herein a metal-free cross-coupling of diazirines with arylboronic acids under oxidative conditions. The reaction affords a series of substituted olefins. It is proposed that the interaction between the nitrogen on diazirine with arylboronic acid plays a key role in this transformation.

Asymmetric organocatalytic reduction of ketimines with catecholborane employing a N-triflyl phosphoramide Br?nsted acid as catalyst

The first asymmetric reduction of ketimines with catecholborane employing an enantiopure N-triflyl phosphoramide as the organocatalyst has been developed. Five mole % of the catalyst provides the corresponding secondary amines in very good to almost quantitative yields and good enantioselectivities up to 86:14 e.r. under mild reaction conditions.

Asymmetric hydrogenation of N-alkyl and N-aryl ketimines using chiral cationic Ru(diamine) complexes as catalysts: The counteranion and solvent effects, and substrate scope

Asymmetric hydrogenation of N-alkyl and N-aryl ketimines catalyzed by chiral cationic η6-arene-(N-monosulfonylated diamine) Ru(II) complexes has been investigated. Strong counteranion and solvent effects on the enantioselectivity were observed. The ruthenium catalyst bearing non-coordinating BArF- anion was found to be particularly effective for the hydrogenation of acyclic and exocyclic N-alkyl ketimines in the presence of (Boc)2O in dichloromethane or even under solvent-free conditions, providing chiral amines with up to >99% ee and full conversions. Alternatively, the ruthenium catalyst bearing achiral phosphate anion together with corresponding phosphoric acid as the additive was also efficient for the hydrogenation of N-alkyl ketimines in the absence of (Boc)2O with excellent enantioselectivities and full conversions. For N-aryl ketimines lower enantiomeric excesses were observed by using the ruthenium catalyst bearing BArF- anion. This catalytic protocol thus provides a facile and practical access to optically active amines and has been successfully employed in the gram-scale synthesis of enantiomerically pure (+)-sertraline.

Asymmetric hydrogenation of N-Alkyl ketimines with phosphine-free, chiral, cationic Ru-MsDPEN catalysts

(Solvent) free and easy: A phosphine-free, chiral, cationic Ru-MsDPEN complex [(S,S)-1] is found to be an efficient catalyst for the enantioselective hydrogenation of a range of often-problematic N-alkyl ketimines (see scheme). This new method provides a more practical and greener synthetic approach to optically active amines, particularly N-alkyl amines, such as Sertraline.

Microwave-assisted, Pd(0)-catalyzed cross-coupling of diazirines with aryl halides

Pd(0)-catalyzed cross-coupling reactions of diazirines with aryl halides under microwave heating conditions afford a series of substituted olefins. A reaction mechanism involving the migratory insertion of the Pd carbene intermediate is proposed.

1,1′-Binaphthyldiamine-based lewis bases as readily available and efficient grganocatalysts for the reduction of N-Aryl and N-Alkyl ketimines

The development of simple, low-cost, efficient, and sustainable routes to enantiomerically pure amines is a topic of extraordinary interest, specially in view of future industrial applications. In this context, we wish to report a chemical and stereochemical efficient synthesis of chiral amines through the Lewis base activated trichlorosilane reduction of ketimines. An organocatalyst, easily prepared in a single step through the condensation of picolinic acid and commercially available 1,1′-binaphthyldiamine, is the key element of this metal-free methodology, that allowed the synthesis of chiral secondary and primary amines in high yields and stereose-lectivity. Noteworthy, such catalysts are able to promote the reduction of N-alkyl ketimines, often in quantitative yield and up to 87% enantioselectivity; it: is worth mentioning that for such transformations only one other organocatalytic system has been reported so far.

A highly enantioselective organocatalytic method for reduction of aromatic N-alkyl ketimines

A study has demonstrated the development of a highly enantioselective catalytic method for the reduction of aromatic N-alkyl ketimines by trichlorosilane under mild conditions using the newly designed Lewis base organocatalyst that incorporates C- and S-chirality. The S-chiral sulfinamide group in these catalysts plays a crucial role similar to the carboxamide groups as Lewis base for the activation of HSiCl3, and also serves as a source of chirality that the carboxamide group lacks for the asymmetric induction. The results of the study showed that excellent enantioselectivities of up to 99.6% ee and high yields were obtained for a wide range of substrates. Further works is also in progress to clarify the mechanism of the transformation and explore the full application scope of the present catalyst system.