Action Of Primary Amines Research Articles

A new route to some enantiomerically pure substituted morpholines from d-ribono- and d-gulono-1,4-lactones

d-Ribono-1,4-lactone, after acetalation, tritylation, and reduction, leads to a cyclization compound which gave with tosyl chloride 1,4-anhydro-2,3- O-isopropylidene-5- O-trityl- d-ribitol. The latter was transformed (acid hydrolysis, periodate oxidation, reduction, tritylation, and tosylation) into a ditosylated derivative 16, which was cyclized into morpholines by the action of primary amines. Acid hydrolysis, followed by acetylation, gives the (2 S)-acetoxymethyl-4-isopropyltetrahydro-1,4-oxazine ( 21). A similar sequence has been applied to d-gulonolactone to give access to oxazines 33, 34, and 35.

ChemInform Abstract: Application of New Camphor‐Derived Mercapto Chiral Auxiliaries to the Synthesis of Optically Active Primary Amines.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 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.

Application of New Camphor-Derived Mercapto Chiral Auxiliaries to the Synthesis of Optically Active Primary Amines

A series of enantiomerically pure sulfinimines carrying new camphor- based mercapto chiral auxiliaries are subjected to asymmetric alkyla- tion. Such reaction offers an excellent route to the preparation of optically active primary amines. Also reported here is an unprecedented Grignard addition of a chiral sulfenimine leading to a single enantiomer of the corresponding sulfenamide and thence produced enantiopure amine after acidic aqueous workup. The chiral auxiliary can be recovered in high yield

Catalyzed Enantioselective Borane Reduction of Ketimine Derivatives

The enantioselective borane reduction of imine derivatives is catalyzed by ß-hydroxy sulfoximine 1. Optically active primary and secondary amines are obtained with enantioselectivities of up to 72% ee.

Orthometallated primary amines. Part 1. Facile preparation of the first optically active cyclopalladated primary amines

Reaction of [PdCl2{NH2CH(Me)Ph}2]1 with AgCIO4(1 : 2) gave a solution containing an orthopalladated complex 2. Addition to this solution of neutral ligands or NaBr led to isolation of the complexes [Pd{C6H4[CH(Me)NH2-2]}(L2)]CIO4[L = pyridine 3a, L2= cycloocta-1,5-diene(cod)3b or 2,2′-bipyridine 3c] or [{Pd{C6H4[CH(Me)NH2-2]}(µ-Br)}2]4, respectively. Reaction of 4 with PPh3 or Tl(acac)(Hacac = acetylacetone) gave [Pd{C6H4[CH(Me)NH2-2]}Br(PPh3)]5 or [Pd{C6H4[CH(Me)NH2-2]}(acac)]6, respectively. Complexes 1, 4 and 5 can be obtained optically pure by using (R)-(+)- or (S)-(–)-α-methylbenzylamine as starting material. The solid-state crystal structures of 3b and R-5 were determined at low temperatures. In both complexes the palladium atom adopts the usual square-planar co-ordination. The major angular distortion is associated with the small bite of the chelating ligand (80.8 and 81.2°, respectively). The weaker trans influence of the cod ligand in 3b accounts for ca. 0.02 A longer Pd–N and Pd–C bonds in R-5 than in 3b. Short contacts between the perchlorate anion or bromo ligand in 3b or R-5 with the amino group (N ⋯ O 3.06 or N ⋯ Br 3.41 A, respectively) probably represent hydrogen bonds.

Purines, pyrimidines and condensed systems based on them. 10. Reactivity of 1,3-dimethyl-6-chlorolumazine with respect to amines: Competition of aminodechlorination and aminodehydrogenation reactions

1,3-Dimethyl-6-chlorolumazine reacts with secondary alkylamines and hydrazine to form 1,3-dimethyl-6-amino(hydrazino) derivatives in good yields. At the same time, 6-chloro-7-amino-1,3-dimethyllumazines are formed by the action of primary amines and liquid ammonia, in addition to the nucleophilic substitution products of chlorine.

On the synthesis of 3,4-dihydro-2H-1,2-benzothiazine 1,1-dioxides

The 3,4-dihydro-2H-1,2-benzothiazine 1,1-dioxides were prepared by reduction of the corresponding 1,2-benzothiazin-2-ones with diborane. The latter were obtained by the action of primary amines on 4,5-dimethoxy-2-carbomethoxymethylbenzenesulfonyl chloride followed by basic hydrolysis and cyclization of the formed 4,5-dimethoxy-2-carbomethoxymethylbenezenesulfonamides.

ChemInform Abstract: Asymmetric Reduction of Ketoxime O‐Alkyl Ethers with Chirally Modified NaBH4‐ZrCl4.

Reducing agents prepared from sodium borohydride (NaBH4), zirconium tetrachloride (ZrCl4), and chiral amino alcohols have been successfully applied to the enantioselective reduction of oxime ethers. Optically active primary amines were obtained in high enantiomeric excess (⩽95% e.e.) with good chemical yield. The extent of asymmetric synthesis was dependent on the solvent, the temperature, the structure of chiral amino alcohol, and the proportions [NaBH4] : [ZrCl4] : [chiral amino alcohol] : [oxime ether].

ChemInform Abstract: Chiral Building Blocks for the Synthesis of N‐Containing Natural Products. Part 3. Enantiomerically Pure N‐Boc Protected β‐Keto γ‐Amino Acid Esters from Simple Keto Precursors. A Novel, Stereocontrolled Approach to Statine Derivatives with Any Desired Configuration.

AbstractReaction of the isovalerophenone (I) with (S)‐1‐phenylethylamine (II) and subsequent hydrogenation result in the formation of the chiral secondary amine (III) which is deprotected, yielding the optically active primary amine (IV).

Asymmetric reduction of ketoxime O-alkyl ethers with chirally modified NaBH4–ZrCl4

Reducing agents prepared from sodium borohydride (NaBH4), zirconium tetrachloride (ZrCl4), and chiral amino alcohols have been successfully applied to the enantioselective reduction of oxime ethers. Optically active primary amines were obtained in high enantiomeric excess (⩽95% e.e.) with good chemical yield. The extent of asymmetric synthesis was dependent on the solvent, the temperature, the structure of chiral amino alcohol, and the proportions [NaBH4] : [ZrCl4] : [chiral amino alcohol] : [oxime ether].

Asymmetric reduction of ketoxime O-alkyl ethers with sodium borohydride–Lewis acid

Novel hydride agents formed by combining Lewis acids with sodium borohydride (NaBH4) reduce quantitatively ketoxime O-alkyl ethers to the corresponding optically active primary amines with high enantioselectivities (up to 95% e.e.) in the presence of chiral amino alcohols.

Synthesis and molecular structure of the optically active organoaluminium dimer (S)-(—)-(S)-(—)- [(C 6H 5)CH(CH 3)NHA1(CH 3) 2] 2

Reaction of the optically active primary amine (S)-(—)-α-methylbenzylamine with trimethylaluminium in heptane affords the crystalline organoaluminium dimer (S)-(—)-(S)-(—)-[(C 6H 5)CH(CH 3)NHA1(CH 3) 2] 2. Isolated as large, colourless, extremely air-sensitive prismatic crystals, the title compound crystallizes in the orthorhombic space group P2 12 12 1 with unit cell parameters a = 8.406(3), b = 15.505(4), c = 17.547(5) Å, V = 2287 Å 3 and ϱp = 1.03 g cm −3 for Z = 4. Least-squares refinement based on 1477 observed reflections converged at R = 0.056, R w = 0.058. Methane was eliminated during the course of the reaction due to cleavage of A1C and NH bonds resulting in an asymmetric A1 2N 2 fragment at the core of the organoaluminium dimer. The mean A1C bond distance in the dimethylaluminium units is 1.930(8), while the mean A1N bond distance is 1.950(5) Å. Specific rotation ([α] D 25 in CH 2C1 2)of the dimer is determined to be - 20.6°.

Enantioselective Synthesis of α‐Substituted Primary Amines by Nucleophilic Addition to Aldehyde‐SAMP Hydrazones

The optically active primary amines (R)- or (S)-3 having a center of chirality at the α-position can be obtained from the aldehydes 1 via the SAMP hydrazones (S)-2. Addition of R2Li followed by NN bond cleavage leads in good yields and enantioselectively (ee = 81–94%) to (R)- or (S)-3.

ChemInform Abstract: Asymmetric Catalysis. Part 29. Optically Active Primary Amines by Enantioselective Catalytic Hydrosilylation of Ketoximes.

AbstractAlkyl aryl ketoximes (I) [E/ Z Vmixtures of (I) are used as formed in the syntheses] undergo catalytic hydrosilylation with diphenylsilane (II) to give the silylamines (III) and (IV), which on hydrolysis yield the prim. amines (V) and (VI).

Asymmetric Reduction of Chiral Acetophenone Oxime Ethers to Optically Active Primary Amines

Abstract Chiral oxime ethers were synthesized from Na salt of acetophenone oxime and chiral halides, tosylates, or N-tosylaziridines which were derived from β-pinene or α-amino acids. Asymmetric reduction of the chiral oxime ether with LiAlH4 or BH3·THF gave the optically active primary amine.

Asymmetric catalysis. 29. Optically active primary amines by enantioselective catalytic hydrosilylation of ketoximes

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAsymmetric catalysis. 29. Optically active primary amines by enantioselective catalytic hydrosilylation of ketoximesHenri. Brunner, Richard. Becker, and Sonja. GauderCite this: Organometallics 1986, 5, 4, 739–746Publication Date (Print):April 1, 1986Publication History Published online1 May 2002Published inissue 1 April 1986https://doi.org/10.1021/om00135a020RIGHTS & PERMISSIONSArticle Views579Altmetric-Citations45LEARN 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 (989 KB) Get e-Alerts Get e-Alerts

First Optically Active Heptalenes and their Absolute Configuration

AbstractIt is shown that dimethyl 7‐isopropyl‐5, 10‐dimethylheptalene‐1, 2‐dicarboxylate (1) and dimethyl 5, 6, 8, 10‐tetramethylheptalene‐1, 2‐dicarboxylate (2) can be resolved via the corresponding mono‐acids and with the aid of optically active primary or secondary amines such as 1‐phenylethylamine or ephedrine into the (−)‐(P)‐ and (+)‐(M)‐enantiomeres, respectively. Characteristic for the (P)‐chirality of the heptalene π‐skeleton with C2 or pseudo‐C2 symmetry are two (−)‐CE's at the long wavelength region (450–300 nm) followed by at least one intense (+)‐CE at wavelengths about or below 300 nm. The absolute configuration of the heptalenes was correlated with the well‐established absolute configuration of (+)‐(R)‐ and (−)‐(S)‐1‐phenylethanol.

Obtention d'amino-2 thiazoles-1,3 par action d'amines primaires sur des α-halo β-thiocyanato alcenes

Action of primary amines on vic-halo-thiocyanato alkenes R 1-C(-SCN)=CX-R 2 affords 2-amino 1,3-thiazoles, the cyclisation taking place with migration of the sulphur altom on the CC bond; thus 2-cyclohexylamino 5-propyl 1,3-thiazole is obtained from 2-bromo 1-thiocyanato 1-pentene and cyclohexylamine.

Functional polymers. XIX. Biuret oligomers and polymers of biologically active primary aliphatic amines

AbstractBiuret oligomers and polymers from primary aliphatic amines and aromatic or aliphatic diisocyanates have been synthesized. To demonstrate the feasibility of the synthesis of polybiurets, aliphatic primary amines with n‐propyl, n‐hexyl, n‐octyl, and n‐dodecyl groups have been incorporated. For the synthesis of biuret oligomers of biologically active primary aliphatic amines [8‐(4‐amino‐1‐methylbutylamino)‐6‐methoxyquinoline] (primaquine) and adamantanamine were selected. Primaquine was also incorporated into polyepichlorohydrin by nucleophilic substitution of the chlorine of the chloromethyl group by the primary aliphatic amino group of primaquine. The structure of the biuret polymers was established by elemental analysis, and by infrared 1H‐ and 13C‐NMR spectroscopic characterization. Several attempts to use primaquine as a diamine for the formation of condensation polymers, including reaction of primaquine with sebacoyl chloride (to form polyamides), or with diisocyanates (to form polyureas) were unsuccessful.

Regioselectivity and stereoselectivity in the reaction of cis-1,2,2-Trimethylcyclopentane-1,3-dicarboxylic anhydride (cis-camphoric anhydride) with chiral primary amines

The reaction between primary amines and cis-1,2,2 trimethylcyclopentane-1,3-dicarboxylic anhydride (3) has been shown to be regioselective for the less hindered carbonyl group. Kinetic resolution was observed when racemic primary amines and the (1R,3S) anhydride (3) were used. Similar stereoselectivity was found in the alternative reaction between racemic (3) and optically active primary amines. In both cases, the absolute configuration of the more reactive enantiomeric amine or anhydride could be correlated with a model (7). The use of (3) is recommended for the prediction of the absolute configurations of racemic and optically active primary amines.