Search results for "ASYM"
showing 10 items of 2151 documents
Asymmetric Synthesis of Functionalized Tricyclic Chromanes via an Organocatalytic Triple Domino Reaction
2017
A highly stereoselective triple domino reaction for the synthesis of functionalized tricyclic chromane scaffolds has been developed. A secondary amine-catalyzed domino Michael/Michael/aldol condensation reaction between aliphatic aldehydes, nitro-chromenes, and α,β-unsaturated aldehydes leads to the formation of synthetically important tricyclic chromanes bearing four contiguous stereogenic centers including a tetrasubstituted carbon in good yields (20–66%) and excellent stereoselectivities (>20:1 dr and >99% ee).
Asymmetric Synthesis of Spirobenzazepinones with Atroposelectivity and Spiro-1,2-Diazepinones by NHC-Catalyzed [3+4] Annulation Reactions
2016
A strategy for the NHC-catalyzed asymmetric synthesis of spirobenzazepinones, spiro-1,2-diazepinones, and spiro-1,2-oxazepinones has been developed via [3+4]-cycloaddition reactions of isatin-derived enals (3C component) with in-situ-generated aza-o-quinone methides, azoalkenes, and nitrosoalkenes (4atom components). The [3+4] annulation strategy leads to the seven-membered target spiro heterocycles bearing an oxindole moiety in high yields and excellent enantioselectivities with a wide variety of substrates. Notably, the benzazepinone synthesis is atroposelective and an all-carbon spiro stereocenter is generated.
Hierarchy of Asymmetry at Work: Chain-Dependent Helix-to-Helix Interactions in Supramolecular Polymers.
2018
A detailed investigation of the hierarchy of asymmetry operating in the self-assembly of achiral (1) and chiral ((S)-2 and (R)-3) 1,3,5-triphenylbenzenetricarboxamides (TPBAs) is reported. The aggregation of these TPBAs is conditioned by the point chirality at the peripheral side chains for (S)-2 and (R)-3. An efficient helix-to-helix interaction that goes further in the organization of fibrillar bundles is experimentally detected and theoretically supported only for the achiral TPBA 1. The effective interdigitation of the achiral aliphatic side chains produces a social self-sorting to form preferentially heterochiral macromolecular aggregates.
The effect of disorder on optical spectra of conjugated polymers
1993
Abstract Using the semi-empirical parametrization of the Pariser-Parr-Pople model we determine the excitonic states in conjugated polymers. The employed parameters correspond to a moderate strength of the long-range Coulomb interaction. In order to take the disorder into account, the nearest-neighbour transfer matrix elements are chosen according to a random distribution. Averaging the results over a large number of chains of 100 sites, which are known to be sufficiently long so that finite-size effects become negligible, we obtain the linear and third-order nonlinear optical susceptibilities. With increasing disorder the linear absorption, the two-photon absorption and the third-harmonic g…
Studien zum Vorgang der Wasserstoffübertragung, 73. Die Reduktion prochiraler Alkyl(aryl)ketone zu Carbinolen und Pinakolen mit Alkaliamalgamen
1984
Es werden die Faktoren ermittelt, welche die Stereochemie und das Mengenverhaltnis (C/P) des bei der Reduktion von Acetophenon mit Lithium-, Natrium- und Kaliumamalgam (Li/Hg, Na/Hg, K/Hg) gebildeten Carbinols (C) und Pinakols (P) bestimmen. Das C/P-Verhaltnis wird beeinflust a) durch Protonendonatoren, b) durch quartaren Ammoniumsalze, c) durch bis-tertiare Amine. Bei Anwesenheit von optisch aktiven quartaren Ammoniumsalzen und optisch aktiven bis-tertiaren Aminen wird sowohl beim Pinakol als auch beim Carbinol eine geringe optische Induktion beobachtet. Bei der Reduktion von Pivalophenon mit Li/Hg entsteht das anomale Dimerisierungsprodukt 20. Studies on the Occurrence of Hydrogen Transfe…
Simulation of first- and second-order transitions in asymmetric polymer mixtures
1993
The critical properties of dense asymmetric binary polymer mixtures are studied by grand canonical simulations within the framework of the 3-dimensional bond fluctuation lattice model. The monomers interact with each other via a potential ranging over the entire first peak of the pair distribution. An asymmetry is realized by giving the ratio of interactions λ = ∈AA/∈BB between monomers of the A-species and of the B-species a value different from 1. Using multiple histogram extrapolation techniques for the data analysis, the two phase region, which is a line of first-order transitions driven by the chemical potential difference, and the critical point are determined for a mixture of chains …
LC-Polymers with Axial Chirality
1991
Abstract Liquid crystalline polymers with axial chirality are prepared. These polymers are chiral, not due to a single asymmetric carbon atom, but due to a larger molecular fragment, which is chiral as a whole. They exhibit cholesteric and chiral smectic C* phases. Dielectric spectroscopy proves strong ferroelectric properties in the chiral smectic C* phases of these polymers.
Stereoselective synthesis of perillaldehyde-based chiral β-amino acid derivatives through conjugate addition of lithium amides.
2014
The Michael addition of dibenzylamine to (+)-tert-butyl perillate (3) and to (+)-tert-butyl phellandrate (6), derived from (S)-(−)-perillaldehyde (1), resulted in diastereomeric β-amino esters 7A–D in a moderately stereospecific reaction in a ratio of 76:17:6:1. After separation of the diastereoisomers, the major product, cis isomer 7A, was quantitatively isomerized to the minor component, trans-amino ester 7D. All four isomers were transformed to the corresponding β-amino acids 10A–D, which are promising building blocks for the synthesis of β-peptides and 1,3-heterocycles in three steps. The steric effects of the isopropyl group at position 4 and of the α-methyl substituent of (R)-N-benzyl…
ChemInform Abstract: Stereoselective Synthesis of α-Arylalkylamines by Glycosylation-Induced Asymmetric Addition of Organometallic Compounds to Imine…
2009
Arylalkylamines are of interest as building blocks for the synthesis of biologically active compounds and as chiral ligands or chiral auxiliaries in stereoselective syntheses [1]. Their stereoselective synthesis has been achieved by enantioselective reduction of ketimines using chiral reagents [2], as for example Corey’s oxaborolidines [3], or proline-derived triacyloxyborohydrides [4]. Particularly efficient asymmetric syntheses of chiral arylalkylamines have been accomplished by Noyori et al. [5] through enantioselective catalysis of hydrogen transfer reactions using a chiral 1,2-diphenyl-ethylenediamine ruthenium catalyst. Enantioselective transferhydrogenationshave also been achieved us…
Stereoselective Synthesis of α-Arylalkylamines by Glycosylation-induced Asymmetric Addition of Organometallic Compounds to Imines
2009
Arylalkylamines are of interest as building blocks for the synthesis of biologically active compounds and as chiral ligands or chiral auxiliaries in stereoselective syntheses [1]. Their stereoselective synthesis has been achieved by enantioselective reduction of ketimines using chiral reagents [2], as for example Corey’s oxaborolidines [3], or proline-derived triacyloxyborohydrides [4]. Particularly efficient asymmetric syntheses of chiral arylalkylamines have been accomplished by Noyori et al. [5] through enantioselective catalysis of hydrogen transfer reactions using a chiral 1,2-diphenyl-ethylenediamine ruthenium catalyst. Enantioselective transferhydrogenationshave also been achieved us…