Amination Of Aldehydes Research Articles

Facile Reductive Amination of Aldehydes with Electron-Deficient Anilines by Acyloxyborohydrides in TFA: Application to a Diazaindoline Scale-Up

ADVERTISEMENT RETURN TO ISSUEPREVAddition/CorrectionORIGINAL ARTICLEThis notice is a correctionFacile Reductive Amination of Aldehydes with Electron-Deficient Anilines by Acyloxyborohydrides in TFA: Application to a Diazaindoline Scale-UpEric E. Boros*, James B. Thompson, Subba R. Katamreddy, and Andrew J. CarpenterCite this: J. Org. Chem. 2009, 74, 22, 8908Publication Date (Web):October 28, 2009Publication History Published online28 October 2009Published inissue 20 November 2009https://doi.org/10.1021/jo9022342Copyright © 2009 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views1170Altmetric-Citations-LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (543 KB) Get e-AlertsSUBJECTS:Aldehydes,Amines,Carbonyls,Organic reactions,Sodium Get e-Alerts

Direct One-Pot Reductive Amination of Aldehydes with Nitroarenes in a Domino Fashion: Catalysis by Gum-Acacia-Stabilized Palladium Nanoparticles

This note describes the direct reductive amination of carbonyl compounds with nitroarenes using gum acacia-palladium nanoparticles, employing molecular hydrogen as the reductant. This methodology is found to be applicable to both aliphatic and aromatic aldehydes and a wide range of nitroarenes. The operational simplicity and the mild reaction conditions add to the value of this method as a practical alternative to the reductive amination of carbonyl compounds.

Novel Combination of Sodium Borohydride and Reusable Polyaniline Salt Catalyst for Rapid and Efficient Reductive Amination of Carbonyl Compounds

A simple, fast and efficient method is developed for reductive amination of anthraldehydes and naphthaldehydes in a single step. In this method, sodium borohydride is used in combination with reusable polyaniline salt (PANI) catalyst for the first time. The reductive amination of anthraldehydes with amines was carried out in DCM-MeOH (3:1) solvent mixture at room temperature using NaBH4/PANI system. This method afforded the amines in excellent yields immediately without any side product. This method was successfully extended for the reductive amination of benzaldehyes, heterocyclic aldehydes, α,β-unsaturated aldehydes and ketones. Polyaniline salt catalyst is recoverable and reusable without losing its potency. In this method, we have established the use of various polyaniline salts containing mineral, solid/liquid organic protonic acid prepared by aqueous/emulsion polymerization pathway as polymer based solid acid catalyst in the reduction amination reaction.

Reductive Amination of Aldehydes and Ketones Under Heterogeneous and Solvent-Free Conditions Using Sodium-Borohydride and Silica-Gel–Supported Sulfuric Acid

A regioselective and convenient procedure for preparation of amines by reductive amination of aldehydes and ketones using sodium borohydride in the presence of sulfuric acid supported on silica gel as an active, inexpensive, and recoverable catalyst under heterogeneous and solvent-free conditions at room temperature is described.

Asymmetric α-Amination of Aldehydes and Ketones Catalyzed by tert-Butoxy-L-Proline

Asymmetric electrophilic α-amination of aldehydes and ketones is described using trans-3-tert-butoxy-Lproline and trans-4-tert-butoxy-L-proline as efficient catalysts. Good yields and high enantioselectivities are obtained working at 0°C or at room temperature with a catalyst loading of only 5 mol%.

ChemInform Abstract: Reductive Amination of Aldehydes and Ketones to Their Corresponding Amines with N‐Methylpyrrolidine Zinc Borohydride.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Nickel-catalyzed multi-component coupling reaction of aldimine, alkyne, and dimethylzinc via dimerization of butadiene

In the presence of a Ni/phosphine ligand catalyst, dimethylzinc, alkyne, butadiene, aldehyde, and primary amine were successively combined via dimerization of butadiene to provide (3 E,7 E,10 Z)-dodecatrienylamine in good yields with excellent regio and stereoselectivities.

Facile Reductive Amination of Aldehydes with Electron-Deficient Anilines by Acyloxyborohydrides in TFA: Application to a Diazaindoline Scale-Up

A scale-up of diazaindoline 1 was achieved in four stages and 32% overall yield. The key step involved rapid reductive amination of aldehyde 8 with aniline 5 by sodium triacetoxyborohydride (STAB-H) and TFA followed by ring closure of intermediate amine 9 to compound 1 in the same pot. These reaction conditions were also applied to facile reductive aminations with anilines known to have little reactivity under STAB-H/AcOH conditions. Spectral data supported the tris(trifluoroacetoxy)borohydride anion (16) as the active reducing agent.

Synthesis and application of amphoteric starch graft polymer

An amphoteric starch-graft-polyacrylamide (S-g-PAM) was prepared by inverse emulsion polymerization, subsequent hydrolysis reaction and Mannich reaction. The copolymerization was carried out using ammonium persulfate and urea as redox initiator. The reaction conditions and application as flocculant were investigated. Experiments showed that in hydrolysis reaction, a stable emulsion of anionic S-g-PAM with high hydrolysis degree could be obtained in a shorter time when sodium carbonate and sodium hydroxide were used together as hydrolyzing agents. In Mannich reaction, after pre-formation of an aldehyde–amine adduct was added to the anionic emulsion product, the amination degree of amphoteric S-g-PAM could reach 43.6% and the highest solution viscosity was obtained. The application test showed that the results of treatment of several kinds of industrial waste water by amphoteric S-g-PAM were better than those treated with cationic polyacrylamide (PAM), hydrolytic PAM and amphoteric PAM.

A Yb(OTf)3/PEG-Supported Quaternary Ammonium Salt Catalyst System for a Three-Component Mannich-Type Reaction in Aqueous Media

A one-pot, three-component Mannich reaction of cyclohexanone with aromatic aldehyde and aromatic amine was efficiently catalyzed by Yb(OTf)3/PEG-supported quaternary ammonium salt system in water at room temperature. This reaction afforded the corresponding β-amino carbonyl compounds in good yields with high anti selectivity, and the catalyst system was recyclable.

Micellar media catalyzed highly efficient reductive amination of carbonyl compounds with bis(triphenylphosphine)(tetrahydroborato)zirconium(II), [Zr(BH4)2(Ph3P)2], as a new and a highly water tolerant tetrahydroborate reducing agent

Micellar media under neutral conditions catalyzed successful reductive amination of aldehydes and ketones by bis(triphenylphosphine)(tetrahydroborato)zirconium(II), [Zr(BH4)2(Ph3P)2], as a newly developed hydride transfer agent and a highly water tolerant tetrahydroborate reagent.

Solvent-free direct reductive amination by catalytic use of an organotin reagent incorporated on an ionic liquid

An organotin reagent supported on an ionic liquid was used as a highly effective catalyst (down to 0.1 mol%) for the direct reductive amination of aldehydes and ketones using PhSiH3; this solvent-free method facilitates purification of the products, thus minimizing the contamination by tin.

Preparation and characterization of an immunogenic meningococcal group A conjugate vaccine for use in Africa

Periodic epidemics of group A meningococcal (Mn A) meningitis continue to occur in sub-Saharan Africa. For its prevention, a Mn A polysaccharide (PS)–tetanus toxoid (TT) conjugate vaccine was developed using reductive amination of polysaccharide aldehydes and toxoid hydrazides. In mouse immunization studies, a schedule of three bi-weekly s.c. immunizations of 0.1 or 1 μg of the conjugate (PS content) without an adjuvant induced serum antibody levels of >10,000 units/mL measured by enzyme-linked immunosorbent assay (ELISA) as compared to ∼100 units/mL in PS control mice. The elicited antibodies were active in bactericidal assays using either baby rabbit or human complement (titers >1500 compared to ∼200 for the PS control group). The synthesis process is reproducible and scalable, and has been successfully used for manufacturing a Mn A PS–TT conjugate vaccine based on a paradigm of shared manufacturing with transfer of new technology [Jodar L, LaForce FM, Ceccarini C, Aguado T, Granoff DM. Meningococcal conjugate vaccine for Africa: a model for development of new vaccine for the poorest countries. Lancet 2003, 361:1092–4]. A phase 1 clinical trial of the manufactured Men A–TT conjugate vaccine has been successfully carried out in adults in India, and a phase 2 clinical trial in young children is currently underway in Africa.

Reductive Amination of Aldehyde 2,4-Dinitorophenylhydrazones Using 2-Picoline Borane and High-Performance Liquid Chromatographic Analysis

A new method for the determination of carbonyls in air using 2,4-dinitrophenylhydrazine (DNPH) has been developed. The traditional method for the measurement of carbonyl compounds, using DNPH to form the corresponding 2,4-dinitrophenylhydrazone (DNPhydrazone) derivatives, is subject to analytical errors because DNPhydrazones form both E- and Z-geometrical isomers as a result of the C=N double bond. To overcome this issue, a method for transforming the C=N double bond into a C-N single bond, using reductive amination of DNPhydrazone derivatives, has been developed. Reductive amination of aldehyde DNPhydrazones was carried out by adding 2-picoline borane acetonitrile solution in eluate through the DNPH-cartridge. The amination reactions of C(1)-C(10) aldehyde DNPhydrazones were completely converted into the reduced forms within 40 min in the presence of 1 mmol/L 2-picoline borane and 20 mmol/L of phosphoric acid. These reduced forms were very stable and did not change when stored for 2 weeks at room temperature. The absorption maximum wavelengths of the reduced forms from C(1)-C(10) aldehyde DNPhydrazones were 351-352 nm and shifted 6-7 nm toward shorter wavelengths when compared to the corresponding DNPhydrazones, and the molar absorption coefficients were 1.5 x 10(4) (C(1)) to 2.2 x 10(4) L/mol/cm (C(10)). Complete separation between C(1)-C(10) aldehyde DNPhydrazones and the corresponding reduced forms can be achieved by operating the HPLC in gradient mode using an Ascentis RP-Amide column (150 mm x 4.6 mm i.d.). The RSDs of DNPhydrazone (Z + E) peak areas ranged from 0.40-0.66 and those of the corresponding reduced forms ranged from 0.26-0.41. It was shown that the reductive amination method gave improved HPLC analytical precision because of the absence of isomers.

Reductive amination of aldehydes and ketones to their corresponding amines with N-methylpyrrolidine zinc borohydride

A simple and convenient procedure for reductive amination of aldehydes and ketones using N-methylpyrrolidine zinc borohydride (ZBHNMP) as a reducing agent is described. The reactions are carried out with 1 equiv of amine and 1 equiv of aldehyde or ketone using 1 equiv of ZBHNMP in methanol under neutral conditions at room temperature.

Preparation of monodisperse and size-controlled poly(ethylene glycol) hydrogel nanoparticles using liposome templates

Liposomes were used as templates to prepare size-controlled and monodisperse poly(ethylene glycol) (PEG) hydrogel nanoparticles. The procedure for the preparation of PEG nanoparticles using liposomes consists of encapsulation of photopolymerizable PEG hydrogel solution into the cavity of the liposomes, extrusion through a membrane with a specific pore size, and photopolymerization of the contents inside the liposomes by UV irradiation. The size distributions of the prepared particles were 1.32 ± 0.16 μm (12%), 450 ± 62 nm (14%), and 94 ± 12 nm (13%) after extrusion through membrane filters with pore sizes of 1 μm, 400 nm, and 100 nm, respectively. With this approach, it is also possible to modify the surface of the hydrogel nanoparticles with various functional groups in a one-step procedure. To functionalize the surface of a PEG nanoparticle, methoxy poly(ethylene glycol)–aldehyde was added as copolymer to the hydrogel-forming components and aldehyde-functionalized PEG nanoparticles could be obtained easily by UV-induced photopolymerization, following conjugation with poly- l-lysine-FITC through amine–aldehyde coupling. The prepared PEG particles showed strong fluorescence from FITC on the edge of the particles using confocal microscopy. The immobilization of biomaterials such as enzymes in hydrogel particles could be performed with loading β-galactosidases during the hydration step for liposome preparation without additional procedures. The resorufin produced by applying resorufin β- d-galactopyranoside as the substrate showed the fluorescence under the confocal microscopy.

One-Pot, Three-Component Uncatalyzed Quantitative Synthesis of New Aminonaphthols (Betti Bases) in Water

One-pot, three-component reaction of 2-naphthol, aromatic aldehyde, and heteroaryl amine in water at room temperature leads to the formation of the corresponding aminonaphthols (Betti bases). Reaction details and study of enantiomeric resolution of 1-(p-methylphenyl (2-pyrazinylamino) methyl) naphthalene-2-ol with the aid of 1H NMR spectroscopy using chiral europium shift reagent is presented.

Highly Chemoselective Reductive Amination of Carbonyl Compounds Promoted by InCl3/Et3SiH/MeOH System

A new strategy has been developed for reductive amination of aldehydes and ketones with the InCl3/Et3SiH/MeOH system, which is a nontoxic system with highly chemoselective and nonwater sensitive properties. The methodology can be applied to a variety of cyclic, acyclic, aromatic, and aliphatic amines. Functionalities including ester, hydroxyl, carboxylic acid, and olefin are found to be stable under our conditions. The reaction shows a first-order kinetics profile with respect to both InCl3 and Et3SiH. Spectroscopic techniques such as NMR and ESI-MS have been employed to probe the active and resulting species arising from InCl3 and Et3SiH in MeOH, which are important in deriving a mechanistic proposal. In the ESI-MS studies, we have first discovered the existence of stable methanol-coordinated indium(III) species which are presumably responsible for the gentle generation of indium hydride at room temperature. The solvent attribution was crucial in tuning the reactivity of [In-H] species, leading to the establishment of mild reaction conditions. The system is superior in flexible tuning of hydride reactivity, resulting in the system being highly chemoselective.

ChemInform Abstract: Direct Reductive Amination of Aldehydes and Ketones with 2,4‐Ionene‐Based Borohydride Exchange Resin as a Novel Polymer‐Supported Reducing Agent.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Highly chemoselective reductive amination-coupling by one-pot reaction of aldehydes, HMDS and NaBH 4

An efficient and highly chemoselective synthesis of symmetrical secondary amines via reductive amination of aldehydes with inexpensive and commercially available HMDS and sodium borohydride in high to quantitative yields is reported.