Search results for "Absolut"
showing 10 items of 551 documents
Arabinosylamine in Asymmetric Syntheses of Chiral Piperidine Alkaloids.
2004
The stereodifferentiating potential of arabinosyl aldimines was utilized in stereoselective syntheses of 2-substituted dehydropiperidinones and their further transformation to 2,6-cis-substituted piperidinones. The absolute configuration was proven by X-ray analysis and by the synthesis of the enantiomerically pure alkaloid (+)-dihydropinidine. The presented method offers the possibility to synthesize piperidine derivatives enantiomeric to those obtained by the application of the corresponding galactosylamine auxiliary.
Stereoselective Synthesis of 8,12-Furanoeudesmanes from Santonin. Absolute Stereochemistry of Natural Furanoeudesma-1,3-diene and Tubipofurane.
1996
Ketobutenolide 3, easily obtained from santonin (1), has been transformed into two natural furanoeudesmanes 4 and 5, isolated from Commiphora molmol and Tubipora musica, respectively. trans- And cis-decalin systems were obtained by stereoselective reduction of the C(4)-C(5) double bond in 3 in the following way: hydrogenation of 3 over Pd/C followed by acidic treatment gave the cis isomer 10 as the major product; selective hydrogenation of the C(1)-C(2) double bond with the Wilkinson's catalyst followed by reduction with NaTeH yielded mainly the trans isomer 9. Compounds 9 and 10 were transformed into 4 and 5 in parallel sequences. Optical rotation and CD measurements of the synthetic produ…
Rearrangement of Germacranolides. Synthesis and Absolute Configuration of Elemane and Heliangolane Derivatives from Cnicin
2003
A study of the Cope rearrangement of 15-oxo-germacranolides to 15-oxo-elemanolides has been carried out. The synthesis of two natural elemanolides, isolated from Centaurea paui, and an efficent isomerization of the C-4/C-5 double bond of 15-oxo-germacranolides to form heliangolides are reported. The absolute configuration of all the compounds has been ascertained. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Effect of addition of Lewis/Brönsted acids in the asymmetric aldol condensation catalyzed by trifluoroacetate salts of proline-based dipeptides
2012
Abstract Proline-based dipeptides catalyze aldol condensations with good yield and stereoselectivity after addition of zinc or sodium acetate to the trifluoroacetate peptide. The chirality of the N-terminal proline in the catalyst determines the absolute configuration of the aldol product, but stereoselectivity depends on the configuration of both amino acids, and is higher for the enantiomeric pair R–S, S–R. Regarding the nature of the second component, optimal results in both yield and stereoselectivity are obtained when neutral unbranched primary amino acids are used.
The structure and stereochemistry of atractyligenin
1966
Abstract The structure of atractyligenin C19H28O4, the nor-diterpenoidic aglycone of atractyloside C30H44O16S2K2 has been substantiated as Ia. The absolute configuration shown in Ia proves it to be a derivative of (−)kaurene.
Structurally diverse second-generation [2.2]paracyclophane ketimines with planar and central chirality: syntheses, structural determination, and eval…
2005
A set of 20 novel [2.2]paracyclophane ketimines with planar and central chirality has been synthesized from enantiomerically pure and racemic 5-acyl-4-hydroxy[2.2]paracyclophane and alpha-branched chiral amines. Their X-ray structures were determined to elucidate the three-dimensional structures and the absolute configuration. The ketimines were used as catalysts in the asymmetric 1,2-addition reactions of diethylzinc with substituted benzaldehydes to furnish chiral alcohols in up to 95 % ee.
Absolute Configuration Determination of 2,3-Dihydro-1H,5H-pyrazolo[1,2-a]pyrazoles Using Chiroptical Methods at Different Wavelengths
2016
A correlation between the absolute configuration and chiroptical properties of nonracemic 1,6,7-trisubstituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazoles was studied. A series of 16 novel representatives were prepared by Cu-catalyzed [3 + 2] cycloadditions of racemic (Z)-2-benzylidene-5-oxopyrazolidin-2-ium-1-ides to tert-butyl (S)-(3-oxopent-4-yn-2-yl)carbamate, and their structures were determined by NMR, VCD, ECD, and X-ray diffraction. A clear correlation between the sign of specific rotation and configuration at position C(1) allows for easy determination of the absolute configuration of 1,6,7-trisubstituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazoles by ECD and NMR. While VCD, requirin…
ChemInform Abstract: Two-Carbon Bridge Substituted Cocaines: Enantioselective Synthesis, Attribution of the Absolute Configuration, and Biological Ac…
2010
In an effort to learn more about the general structure-activity relationships of cocaine with the aim to elucidate those structural features that might confer antagonistic properties to such analogues, we describe herein our synthetic efforts to prepare two-carbon bridge functionalized (methoxylated and hydroxylated) analogues. Our approach makes use of a modification of the classical Willstatter synthesis of cocaine: Mannich type cyclization of acetonedicarboxylic acid monomethyl ester with methylamine hydrochloride and 2-methoxysuccindialdehyde in a citrate buffer solution afforded the 6- and 7-substituted 2-carbomethoxy-3-tropinones 3a,b and 4a,b in approximate yields of 64%. Reduction o…
Struktur-Wirkungs-Beziehungen bei Histaminanaloga, 22. Mitt. Absolute Konfiguration und histaminartige Wirkung der enantiomeren α, Nα-Dimethylhistami…
1980
Es werden die Synthesen der enantiomeren α, Nα-Dimethylhistamine (+)—3 und (−)—3, die Ableitung der absoluten Konfiguration sowie die histaminartige Wirksamkeit der Enantiomere am Ileum (H1) und Atrium (H2) des Meerschweinchens beschrieben. Structure-Activity Relationship of Histamine Analogues. XXII: Absolute Configuration and Histamine-like Activity of the Enantiomeric α, Nα-Dimethylhistamines The synthesis of the enantiomeric α, Nα-Dimethylhistamines (+)—3 and (−)—3, the determination of the absolute configuration and the histamine-like activity of the enantiomers on the guinea-pig ileum (H1) and atrium (H2) are reported.
Struktur-Wirkungs-Beziehungen bei Histaminanaloga, 23. Mitt. Absolute Konfiguration und histaminartige Wirkung der enantiomeren α-Chlormethylhistamin…
1981
Es wird die histaminartige Wirksamkeit der enantiomeren α-Chlormethylhistamine (+)-2a und (−)-2a sowie der Nα-Methyl-α-chlormethylhistamine (+)-2b und (−)-2b am Ileum (H1) und Atrium (H2) des Meerschweinchens beschrieben und die absolute Konfiguration der Enantiomere abgeleitet. Structure-Activity Relationships of Histamine Analogues, XXIII: Absolute Configuration and Histamine-like Activity of the Enantiomeric α-Chloromethylhistamines and Nα-Methyl-α-chloromethylhistamines The histamine-like activities of the enantiomeric α-chloromethylhistamines (+)-2a and (−)-2a and of the Nα-methyl-α-chloromethylhistamines (+)-2b and (−)-2b on the guinea pig ileum (H1) and atrium (H2) are reported. The …