Search results for "Isomer"
showing 10 items of 1308 documents
Biomolecular-solvent stereodynamic coupling probed by deuteration.
1983
Thermodynamic interpretation of experiments with isotopically perturbed solvent supports the view that solvent stereodynamics is directly relevant to thermodynamic stability of biomolecules. According with the current understanding of the structure of the aqueous solvent, in any stereodynamic configuration of the latter, connectivity pathways are identifiable for their topologic and order properties. Perturbing the solvent by isotopic substitution or, e.g., by addition of co-solvents, can therefore be viewed as reinforcing or otherwise perturbing these topologic structures. This microscopic model readily visualizes thermodynamic interpretation. In conclusion, the topologic stereodynamic str…
EFFECTS OF DIETARY 18:3 N-3 TRANS ISOMERS ON THE ?6 DESATURATION OF ?-LINOLENIC ACID
1995
Trans isomers of polyunsaturated fatty acids (PUFA) are formed during heat treatment of oils. In the present work, the effect of dietary geometrical isomers of α-linolenic acid (18:3 n-3) on the Δ6 desaturation of all cis 18:3 n-3 was investigated, using rat liver microsomes. The desaturation rates were higher in microsomes from animals fed a cis n-3 deficient diet, as compared to those from the control group or those from rats fed 18:3 n-3 and its trans isomers. These data and the incorporation of long chain trans PUFA in microsomal lipids suggest that geometrical isomers of 18:3 n-3 are probably slowly desaturated and elongated into long chain trans polyunsaturated fatty acids compared to…
The skeletal isomerization of but-1-ene catalyzed by theta-1 zeolite
2001
The complete mechanism for the skeletal isomerization of but-1-ene catalyzed by theta-1 zeolite was investigated theoretically by means of DFT calculations, and the influence of the local geometry of the active site and of electrostatic effects on the geometries of the species involved and on activation and reaction energies were analyzed. It was found that whereas the geometry and stability of alkoxide intermediates are strongly influenced by the local geometry of the active site, the ionic transition states are mainly stabilized by electrostatic effects. Both aspects result in a lowering of the activation energies of the elementary steps that form the mechanism and therefore in enhanced r…
Experimental and theoretical investigations for the regio and stereoselective transformation of trans 1,2,3-trisubstituted aziridines into trans oxaz…
2003
The regio and stereoselective transformation of trans 1,2,3-trisubstituted aziridines into trans oxazolidin-2-ones takes place in good yield. However, the cis configuration at C2 and C3 in monocyclic aziridines is a limiting factor for this transformation. Ab initio calculations show that while the ring-opening process assisted by iodide is regioselective, the subsequent ring-closure is responsible for the retention of the configuration at the trans oxazolidin-2-ones. The larger energy found for the ring-closure process for the cis aziridines accounts for the non-formation of the cis oxazolidin-2-ones.
Stereoselective synthesis of 7,11-guaien-8,12-olides from santonin. Synthesis of podoandin and (+)-zedolactone A.
2000
Photochemical rearrangement of hydroxy ester 2, easily obtained from santonin (1), afforded butenolide 4, a good starting material for the synthesis of 7,11-guaien-8,12-olides. Compound 4 has been transformed into compound 10, which has been used for the synthesis of podoandin (5) and (+)-zedolactone A (ent-6). Regioselective elimination of the acetyl group on C10 afforded directly podoandin (5). For the synthesis of ent-6, a hydroxyl group has been regio- and stereoselectively introduced at the 4alpha-position through the 3alpha,4alpha-epoxide 15. The basic hydrolysis of the 10-acetyl group in compound 18 took place with concomitant intramolecular conjugated addition of the alkoxide to the…
NonclassicalPschorr andSandmeyer Reactions in Pyrazole Series
2005
The diazonium salt derived from 4-amino-N,1,3-trimethyl-N-(3-methyl-1-phenyl-1H-pyrazol-5-yl)-1H-pyrazole-5-carboxamide (14) was reacted with a mixture of CuSO4 and NaCl, with ascorbic acid as an initiator to afford the planar derivative 4,6-dihydro-1,4,6,8-tetramethyl-3-phenyldipyrazolo[3,4-b:4′,3′-d]pyridin-5(3H)-one (16) and its unexpected isomer 4,6-dihydro-3,4,6,8-tetramethyl-1-phenyldipyrazolo[4,3-b:4′,3′-d]pyridin-5(1H)-one (17), as well as the epimers (3S,4S)- (or (3S,4R)-) and (3S,4R)- (or (3S,4S)-) 4-chloro-2,4-dihydro-1′,3′,5,5′-tetramethyl-2-phenylspiro[pyrazole-3,4′(1′H)-pyrrolo[3,4-c]pyrazol]-6′(5′H)-one (18a and b, respectively). Epimers 18a and b were converted under basic c…
Asymmetrically substituted calix[4]arenes; A two-dimensional 1H NMR study of a tetraester derivative in the cone-conformation
1991
Abstract Several new chiral calix[4]arenes with three or four different substituents in the p-position have been prepared by fragment condensation. Standard derivatization procedures always led to the formation of mixtures of various conformational isomers from which the derivative in the cone-conformation could be isolated only by preparative HPLC. For a tetraester derivative it was shown by two-dimensional 1H NMR spectroscopy, that due to the different substituents the cone-conformation is strongly distorted. The sodium complex of this tetraester, however, assumes a regular cone-conformation again.
Silica-Immobilized NHC-Gold(I) Complexes: Versatile Catalysts for the Functionalization of Alkynes under Batch and Continuous Flow Conditions
2017
Immobilized sterically demanding NHC-Au(I) complexes silica-[(IPrR)Au]Cl and silica-[(IAdPrR)Au]Cl are synthesized and characterized. These complexes are suitable catalysts in typical homogeneous Au(I)-catalyzed alkyne reactions such as hydration, hydroamination, hydroarylation, or cycloisomerization. The results obtained with the immobilized catalysts in reactions in batch are comparable to those obtained with their homogeneous counterparts with the advantage of easily recovered and recycled in successive reactions. Their catalytic activity decreases when reused in batch reactions, probably because of crushing that is associated with magnetic stirring. In contrast, these immobilized cataly…
Restricted rotation in unbridged sandwich complexes: rotational behavior of closo-[Co(eta 5-NC4H4)(C2B9H11)] derivatives.
2005
Rotation about the centroid/ metal/centroid axis in ferrocene is facile; the activation energy is 1-5 kcal mol - 1 . The structurally similar sandwich complexes derived from closo-[3-Co(η 5 -NC 4 H 4 )-1,2-C 2 B 9 H 1 1 ] (1) have a different rotational habit. In 1, the cis rotamer in which the pyrrolyl nitrogen atom bisects the carboranyl cluster atoms is 3.5 kcal mol - 1 more stable in energy than the rotamer that is second lowest in energy. This cis rotamer is wide, spanning 216°, and may be split into three rotamers of almost equal energy by substituting the N and the carboranyl carbon atoms adequately. To support this statement, closo-[3-Co(η 5 -NC 4 H 4 )-1,2-(CH 3 ) 2 -1,2-C 2 B 9 H …
Thermal Rearrangements of Perchlorohexatrienes-Structures and Experimental and Theoretical Evaluation of Pathways to Isomerization and Cyclization
2009
We have prepared trans- (1) and cis-octachloro-1,3,5-hexatriene (2) by known routes and studied their thermal behavior experimentally and theoretically by ab initio calculations. The three double bonds in 1 and 2 are completely decoupled due to steric hindrance by the eight Cls, as indicated by calculations as well as the single-crystal X-ray structure of 1. The cis isomer 2 can be isomerized to the trans isomer 1 by heating it to 220–250 °C either neat or dissolved in high-boiling solvents, leading to a roughly 2:1 mixture of trans and cis isomers. Calculations at several different levels of theory predict 1 and 2 to be isoenergetic within 2 kJ mol–1. Unimolecular cis/trans isomerization i…