Vicinal Diamines Research Articles

Signal separation and determination of the enantiomeric purity of primary amines with (−)-myrtenal – a 13C NMR study

The applicability of (−)-myrtenal as a chiral derivatizing agent in combination with 13C NMR spectroscopy was investigated. 13C NMR was found to be a valuable tool for the identification and enantiomer differentiation of primary amines including β-amino alcohols and vicinal diamines. The enantiomeric excess could be determined via automated deconvolution and integration, and was found to be in good accordance with the expected values even in the cases, when enantiomer differentiation was not possible in 1H NMR spectra.

A Facile Synthesis of Vicinal Diamines Promoted by Low‐Valent Niobium: Preparation of Chiral Octahydrobiisoquinolines and Their Application to Catalytic Asymmetric Synthesis.

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, please click on HTML or PDF.

Samarium Diiodide‐Induced Intramolecular Pinacol Coupling of Dinitrones: Synthesis of Cyclic cis‐Vicinal Diamines.

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, please click on HTML or PDF.

Synthesis of hindered chiral guanidine bases starting from ( S)-( N, N-dialkyl-aminomethyl)pyrrolidines and BrCN

An efficient method for the preparation of hindered chiral guanidines using cyanogen bromide is described. The reaction between BrCN and vicinal diamines derived from ( S)-2-( N, N-dialkyl-aminomethyl)-pyrrolidines provides chiral substituted cyanamides. The cyanamide derivatives reacted with secondary amines in hexafluoroisopropanol at reflux to form chiral hindered guanidines, which were isolated in good to excellent yields (70–96%). The chiral guanidines were prepared in an effort to design sophisticated chiral guanidine catalysts for asymmetric synthesis.

Vicinal Diamino Functionalities as Privileged Structural Elements in Biologically Active Compounds and Exploitation of their Synthetic Chemistry

The chemistry, synthetic routes and medicinal properties of vicinal diamines and imidazolines are discussed. Synthetic routes towards chemically and pharmaceutically important molecules containing vicinal diamine functionality are discussed in detail. This mini review article covers the new developments of diamine chemistry between 2000 and 2005.

Copper(II) Acetate Promoted Intramolecular Diamination of Unactivated Olefins.

A concise method for the synthesis of cyclic sulfamides and vicinal diamines is presented. This method is enabled by Cu(OAc)2 and demonstrates a new transformation for this metal. Both five- and six-membered vicinal diamine-containing heterocycles have been synthesized in good to excellent yields, and substrate-based asymmetric induction has been achieved. This is the first reported example of intramolecular diamination of olefins.

A Facile Synthesis of Vicinal Diamines Promoted by Low‐Valent Niobium: Preparation of Chiral Octahydrobiisoquinolines and Their Application to Catalytic Asymmetric Synthesis

AbstractAn efficient homocoupling of imines to give vicinal diamines promoted by low‐valent niobium, generated by treatment of NbCl5 with zinc powder, is described. The desired products were obtained in good to excellent yields. Dihydroisoquinoline derivatives also gave the coupling products with good diastereoselectivities (D,L/meso). Optical resolution of the racemic octahydrobiisoquinolines was achieved and their complexes with CuI used in the catalytic asymmetric oxidative coupling of β‐naphthols. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

Tunable Dendritic Ligands of Chiral 1,2‐Diamine and Their Application in Asymmetric Transfer Hydrogenation.

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Novel Dendritic Ligands of Chiral 1,2‐Diamine and Their Application in Asymmetric Hydrogenation of Simple Aryl Ketones.

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Highly Enantioselective Phase-Transfer-Catalyzed Alkylation of Protected α-Amino Acid Amides Toward Practical Asymmetric Synthesis of Vicinal Diamines, α-Amino Ketones, and α-Amino Alcohols.

Highly Enantioselective Phase-Transfer-Catalyzed Alkylation of Protected α-Amino Acid Amides Toward Practical Asymmetric Synthesis of Vicinal Diamines, α-Amino Ketones, and α-Amino Alcohols.

Synthesis of Chiral Vicinal Diamines by Highly Diastereoselective Three‐Component Phenolic Mannich Reaction: Temperature‐Dependent Stereodivergency.

ChemInformVolume 36, Issue 37 Isocyclic Compounds Synthesis of Chiral Vicinal Diamines by Highly Diastereoselective Three-Component Phenolic Mannich Reaction: Temperature-Dependent Stereodivergency. Christophe Rondot, Christophe Rondot Inst. Chim. Subst. Nat., CNRS, F-91198 Gif-sur-Yvette, Fr.Search for more papers by this authorJieping Zhu, Jieping Zhu Inst. Chim. Subst. Nat., CNRS, F-91198 Gif-sur-Yvette, Fr.Search for more papers by this author Christophe Rondot, Christophe Rondot Inst. Chim. Subst. Nat., CNRS, F-91198 Gif-sur-Yvette, Fr.Search for more papers by this authorJieping Zhu, Jieping Zhu Inst. Chim. Subst. Nat., CNRS, F-91198 Gif-sur-Yvette, Fr.Search for more papers by this author First published: 17 August 2005 https://doi.org/10.1002/chin.200537097Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume36, Issue37September 13, 2005 RelatedInformation

Highly Enantioselective Phase‐Transfer‐Catalyzed Alkylation of Protected α‐Amino Acid Amides Toward Practical Asymmetric Synthesis of Vicinal Diamines, α‐Amino Ketones, and α‐Amino Alcohols.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Tunable dendritic ligands of chiral 1,2-diamine and their application in asymmetric transfer hydrogenation

Tunable dendritic N-mono-sulfonyl ligands have been designed and synthesized via direct N-mono-sulfonylization of the chiral dendritic vicinal diamines and their ruthenium complexes demonstrated high catalytic and recyclable activities with comparable enantioselectivities to Noyori–Ikariya’s TsDPEN-Ru in the asymmetric transfer hydrogenation of an extended range of substrates, such as ketones, keto esters, and olefins.

Copper(II) Acetate Promoted Intramolecular Diamination of Unactivated Olefins

A concise method for the synthesis of cyclic sulfamides and vicinal diamines is presented. This method is enabled by Cu(OAc)2 and demonstrates a new transformation for this metal. Both five- and six-membered vicinal diamine-containing heterocycles have been synthesized in good to excellent yields, and substrate-based asymmetric induction has been achieved. This is the first reported example of intramolecular diamination of olefins.

Novel Dendritic Ligands of Chiral 1,2-Diamine and Their Application in Asymmetric Hydrogenation of Simple Aryl Ketones

Novel dendritic chiral vicinal diamine ligands have been synthesized and a series of dendritic Ru(BINAP)(diamine) catalysts were developed for asymmetric hydrogenation of a variety of simple aryl ketones in good catalyticactivity and high enantioselectivity, as well as facile catalyst recycling. An increase of enantio-selectivities was obtained by using the dendritic catalysts compared with Noyori catalysts under the same conditions in the case of several substrates. Meanwhile, a remarkable structural effect on catalytic activity and enantioselectivity, as well as reuse was observed.

Highly Enantioselective Phase-Transfer-Catalyzed Alkylation of Protected α-Amino Acid Amides toward Practical Asymmetric Synthesis of Vicinal Diamines, α-Amino Ketones, and α-Amino Alcohols

Highly enantioselective alkylation of protected glycine diphenylmethyl (Dpm) amide 1 and Weinreb amide 10 has been realized under phase-transfer conditions by the successful utilization of designer chiral quaternary ammonium salts of type 4 as catalyst. Particularly, remarkable reactivity of the chiral ammonium enolate derived from 1b and 4c allowed the reaction with less reactive simple secondary alkyl halides with high efficiency and enantioselectivity. An additional unique feature of this chiral ammonium enolate is its ability to recognize the chirality of beta-branched primary alkyl halides, which provides impressive levels of kinetic resolution and double stereodifferentiation during the alkylation, allowing for two alpha- and gamma-stereocenters to be controlled. Combined with the subsequent reduction using LiAlH4 in cyclopentyl methyl ether (CPME), this system offers a facile access to structurally diverse optically active vicinal diamines. Furthermore, the optically active alpha-amino acid Weinreb amide 11 can be efficiently converted to the corresponding amino ketone by a simple treatment with Grignard reagents. In addition, reduction and alkylation of the optically active alpha-amino ketone into both syn and anti alpha-amino alcohols with almost complete relative and absolute stereochemical control have been achieved. With (S,S)- and (R,R)-4 in hand, the present approach renders both enantiomers of alpha-amino amides including Weinreb amides readily available with enormous structural variation and also establishes a general and practical route to vicinal diamines, alpha-amino ketones, and alpha-amino alcohols with the desired stereochemistry.

Synthesis of Chiral Vicinal Diamines by Highly Diastereoselective Three-Component Phenolic Mannich Reaction: Temperature-Dependent Stereodivergency

[reaction: see text] A diastereoselective three-component synthesis of chiral o-1,2-diaminoalkyl phenols from an electron-rich phenol, an amine, and a chiral alpha-N,N-dibenzylamino aldehyde is developed. The diastereoselectivity of this phenolic Mannich reaction is temperature-dependent,and either anti or syn diastereomer can be prepared by controlling the reaction conditions. Low reaction temperature (-20 degrees C) favors the formation of anti adduct 1, whereas higher temperature (60 degrees C) under otherwise identical conditions produces mainly the syn isomer.

Highly Diastereoselective and Enantioselective Synthesis of Enantiopure C2‐Symmetrical Vicinal Diamines by Reductive Homocoupling of Chiral N‐tert‐Butanesulfinyl Imines.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Highly Diastereoselective [3+2] Cycloadditions Between Non-Racemic p-Tolylsulfinimines and Iminoesters: An Efficient Entry to Enantiopure Imidazolidines and Vicinal Diaminoalcohols

Readily available p-tolylsulfinimines undergo highly stereoselective [3 + 2] cycloadditions with azomethine ylides generated from α -iminoesters and LDA to produce N-sulfinylimidazolidines. In the presence of Lewis acids, p-tolylsulfinimines react with glycine iminoester enolates to produce N-sulfinylimidazolidines, after cyclization of open chain intermediates. These mechanistically diverse processes take place with excellent regio-, stereo-, and facial selectivities, and the latter is opposite to most known reactions involving sulfinimines. Some of the resulting imidazolidines have been transformed into examples of a novel class of nonsymmetrical vicinal diamines using reductive and/or hydrolytic protocols.

Titanocene‐Catalyzed Coupling of Aromatic Amides in the Presence of Organosilanes: A Novel Route to Vicinal Diamines and a New Class of Amine‐Substituted Oligomers.

AbstractFor Abstract see ChemInform Abstract in Full Text.