Search results for "SELECTIVITY"
showing 10 items of 1148 documents
Photocyclization of a bichromophoric phenol/olefi system substituted at the methylene spacer - Zwitterions versus H-bridged intermediates in the exci…
2002
Photolysis of (E)- and (Z)-2-(1-ethyl-3-phenylpropenyl)phenol (1 and 2) under a variety of conditions produces a mixture of dihydrobenzopyrans 3 and 4, dihydrobenzofuran 5, cyclopropanes 6 and 7, and rearranged olefin 8. Acidic treatment of 1 and 2 gives a mixture of the six-membered ring products 3 and 4. Remarkable differences, associated with the nature of the precursor and the reaction conditions, are observed in the regiochemistry of cyclization and in the stereochemistry of the dihydrobenzopyrans (3/4 ratio). This points in favour of an H-bridged intermediate, rather than a fully zwitterionic species, as the direct precursor of the photocyclized products.
Product selectivity effects during cracking of alkanes at very short and longer times on stream
1996
Abstract Cracking of C 7 , C 10 , C 12 and C 14 n-alkanes, over USY, Beta and ZSM-5 zeolites was carried out in a reaction system which allows to obtain instantaneous conversions at very short times on stream. With this system the influence of operation variables, chain length of the paraffin fed, and catalyst structure on product selectivity was established. Positive and negative effects of catalyst decay on product selectivity were obtained, and this behaviour could be simulated by using a deactivation model in which the rate of deactivation depends on the product concentration. It was observed that olefin/paraffin, branched/normal paraffin, branched/normal olefin ratios and aromatic sele…
Direct oxidation of isobutane to methacrolein over V-MCM-41 catalysts
2004
High vanadium content mesoporous vanado-silicates with MCM-41-like structure, obtained by the atrane route, catalyse the direct oxidation of isobutane to methacrolein with 30% selectivity, and a total dehydrogenation (olefin plus methacrolein) selectivity up to 74%.
Role of the gem-Difluoro Moiety in the Tandem Ring-Closing Metathesis−Olefin Isomerization: Regioselective Preparation of Unsaturated Lactams
2006
Careful selection of the metathesis catalyst, solvent, and reaction conditions allows for the efficient and regioselective synthesis of isomeric fluorinated and nonfluorinated lactam derivatives II and III from precursor amides I through a ring-closing metathesis (RCM) reaction or a tandem RCM-isomerization protocol, respectively. The presence of the gem-difluoro moiety in the starting materials exerts a pivotal effect by directing the isomerization step, making the overall tandem transformation a regioselective process. The scope, limitations, and synthetic usefulness of this protocol are also discussed.
Syntheses with organoboranes. Part 14: Enolization–aldolization of conjugated cyclohexenones via dienolborinates
2002
Abstract Enolization of cyclohex-2-enone ( 1 ), 3-methyl- ( 2 ), 3,5-dimethyl- ( 3 ), 3,5,5-trimethyl- ( 4 ), and 3,4,5,5-tetramethylcyclohex-2-enone ( 5 ) with chlorodicyclohexylborane proceeds by deprotonation at the 6-position. Aldolization of the dienolborinates with benzaldehyde, and acetaldehyde, provides the corresponding anti aldols with 87–95% selectivity. Ketones 4 and 5 undergo competitive deprotonation at the 3-methyl group and aldolization at the 2-position. In contrast, lithium dienolates derived from 4 and 5 gave syn aldols with 95% selectivity.
Palladium-Catalysed Intermolecular Direct C–H Bond Arylation of Heteroarenes with Reagents Alternative to Aryl Halides: Current State of the Art
2022
Abstract: This unprecedented review with 322 references provides a critical up-to-date picture of the Pd-catalysed intermolecular direct C–H bond arylation of heteroarenes with arylating reagents alternative to aryl halides that include aryl sulfonates (aryl triflates, tosylates, mesylates, and imidazole-1-sulfonates), diaryliodonium salts, [(diacetoxy)iodo]arenes, arenediazonium salts, 1-aryltriazenes, arylhydrazines and N’-arylhydrazides, arenesulfonyl chlorides, sodium arenesulfinates, arenesulfinic acids, and arenesulfonohydrazides. Particular attention has been paid to summarise the preparation of the various arylating reagents and to highlight the practicality, versatility, and limit…
1,3-Dipolar cycloaddition of 1H-pyrazinium-3-olate and N1- and C-methyl substituted pyrazinium-3-olates with methyl acrylate: a density functional th…
2011
Abstract A DFT study of the 1,3-dipolar cycloaddition of methyl acrylate to 1H-pyrazinium-3-olate and N1- and C-methyl substituted pyrazinium-3-olates, in the gas phase and in THF, has been carried out at the B3LYP/6-31G(d) level. Two stereoisomeric pathways, endo and exo, and two regioisomeric channels, 2-oxo-3,8-diazabicyclo[3.2.1]octane-6-ester and 7-ester products, have been considered. Thermodynamic and kinetic parameters calculated at room temperature have been analyzed. The regioselectivity has been interpreted using reactivity indices. It is generally found that the exo pathway is preferred and the formation of the 6-esters is dominant. The theoretical data obtained for the cycloadd…
Palladium-Catalyzed Dehydrogenative β’-Arylation of β-Keto Esters under Aerobic Conditions: Interplay of Metal and Brønsted Acids
2012
The Bronsted aids: The first dehydrogenative arylation of β-keto esters with arenes under ambient aerobic conditions is described. Under a Pd(II)/Bronsted acid co-catalytic system, regioselective arylations with alkoxylated arenes and phenols were achieved in good yields, even in gram-scale conditions.
Stereoselective cathodic synthesis of 8-substituted (1R,3R,4S)-menthylamines.
2015
The electrochemical generation of menthylamines from the corresponding menthone oximes equipped with an additional substituent in position 8 is described. Due to 1,3-diaxial interactions a pronounced diastereoselectivity for the menthylamines is found.
Optically Active Hyperbranched Polyglycerol as Scaffold for Covalent and Noncovalent Immobilization of Platinum(II) NCN-Pincer Complexes. Catalytic A…
2004
New optically active hyperbranched polymers have been used as microenvironments as well as scaffolds for noncovalent and covalent immobilization of pincer platinum(II) complexes, respectively. The catalytic activity/selectivity of the incorporated platinum(II) complexes in these polymeric chiral supports was investigated. Chiral amphiphilic hyperbranched polyglycerols with core−shell “nanocapsules” structure, namely (−)-P(G40C160.5) (1) and (+)-P(G73C160.5) (2), have been prepared in two straightforward steps by ring-opening multibranching polymerization (ROMBP) of either (−)- or (+)-glycidol, resulting in (−)-PG40 (Mn = 3000, Mw/Mn = 1.3) or (+)-PG73 (Mn = 5500, Mw/Mn = 1.6), respectively.…