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Kinetic measurements for the thermal rearrangement of 2,2-diphenyl-1-[(E)- styryl]cyclopropane (22a) to 3,4,4-triphenylcyclopent-1-ene (23a) in decalin furnished DeltaHrhom{{-{isom}^{ne }}}$=31.0±1.2kcal mol-1 and DeltaSrhom{{-{isom}^{ne }}}$=-6. 0±2.6e.u. The lowering of DeltaHa? by 20kcal mol-1, compared with the rearrangement of the vinylcyclopropane parent, is ascribed to the stabilization of a transition structure (TS) with allylic diradical character. The racemization of (+)-(S)-22a proceeds with DeltaHrhom{{-{rac}^{ne }}}$=28.2±0.8kcal mol -1 and DeltaSrhom{{-{rac}^{ne }}}$=-5±2e.u., and is at 150 106 times faster than the rearrangement. Seven further 1-(2-arylethenyl)-2,2-diphenylcyclopropanes 22, (E)- and (Z)-isomers, were synthesized and characterized. The (E)-compounds showed only modest substituent influence in their krac (at 119.4) and kisom (at 159.3) values. The lack of solvent dependence of rate opposes charge separation in the TS, but a linear relation of log krac with log p.r.f., i.e., partial rate factors of radical phenylations of ArH, agrees with a diradical TS. The ring-opening of the preponderant s-trans-conformation of 22 gives rise to the 1-exo-phenylallyl radical 26 that bears the diphenylethyl radical in 3-exo-position, and is responsible for racemization. The 1-exo-3-endo-substituted allylic diradical 27 arises from the minor s-gauche-conformation of 22 and is capable of closing the three- or the five-membered ring, 22 or 23, respectively. The discussion centers on the question whether the allylic diradical is an intermediate or merely a TS. Quantum-chemical calculations by Houk etal. (1997) for the parent vinylcyclopropane reveal the lack of an intermediate. Can the conjugation of the allylic diradical with three Ph groups carve the well of an intermediate? Copyright

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Metal catalyst and ligand design,
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Alkenes may be synthesised from (alpha-bromobenzyl)benzyldiphenylphosphonium salts by the action of amine bases. A series of stilbenes was synthesised by the action of N-bromosuccinimide and 2,2,6,6-tetramethylpiperidine directly upon dibenzyldiphenylphosphonium salts. The reaction, essentially a phosphonium analogue of the Ramberg Baecklund displays a similar level of cis selectivity as that shown by the parent sulfone.

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(R)- or (S)-benzyl 4-formyl-2,2-dimethyl-3-oxazolidinecarboxylate (7a) and (R)- or (S)-1,1-dimethylethyl 4-formyl-2,2-dimethyl-3-oxazolidinecarboxylate (7b), readily available from serine, react with Wittig reagents to give alkenes 8.Selective deprotection followed by oxidation of the resulting unsaturated amino alcohols 9 provides vinylglycines 5 of defined configuration (>95percent ee) and double-bond geometry.D-Vinylglycines are obtained from L-serine, and conversely, D-serine gives beta,gamma-unsaturated amino acids with the L configuration.The double-bond geometry is controlled by the nature of the phosphorous ylide employed.The scope and limitations of this new methodology for the preparation of chiral vinylglycines is examined.

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Readily prepared cis-beta-(alpha?,alpha?-dimethyl)-4?-methindolylstyrenes undergo acid-catalyzed intramolecular hydroindolation to afford tetrahydrobenzo[cd]indoles. Our experimental and computational investigations suggest that dispersive interactions between the indole and styrene preorganize substrates such that 6-membered ring formation is preferred, apparently via concerted protonation and C-C bond formation. When dispersion is attenuated (by a substituent or heteroatom), regioselectivity erodes and competing oligomerization predominates for cis substrates. Similarly, all trans-configured substrates that we evaluated failed to cyclize efficiently.

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Metal catalyst and ligand design,
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Benzyl<2-(N,N-dimethylamino)phenyl>diphenylphosphonium bromide (3) undergoes alkaline cleavage in 1:1 dioxan-water 1.1*103 times more rapidly (at 37.7 deg C) than benzyl<4-(N,N-dimethylamino)phenyl>diphenylphosphonium bromide < which gives toluene (100percent) as the hydrocarbon product>.

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This invention relates to benzodiazepine derivatives, compositions comprising therapeutically effective amounts of those benzodiazepine derivatives and methods of using those derivatives or compositions in treating cognitive impairment associated with central nervous system (CNS) disorders. In particular, it relates to the use of a alpha5- containing GABAA receptor agonist (e.g., a alpha5-containing GABAA receptor positive allosteric modulator) as described herein in treating cognitive impairment associated with central nervous system (CNS) disorders in a subject in need or at risk thereof, including, without limitation, subjects having or at risk for age-related cognitive impairment, Mild Cognitive Impairment (MCI), amnestic MCI (aMCI), Age- Associated Memory Impairment (AAMI), Age Related Cognitive Decline (ARCD), dementia, Alzheimer’ s Disease(AD), prodromal AD, post traumatic stress disorder (PTSD), schizophrenia, bipolar disorder, amyotrophic lateral sclerosis (ALS), cancer-therapy-related cognitive impairment, mental retardation, Parkinson’ s disease (PD), autism spectrum disorders, fragile X disorder, Rett syndrome, compulsive behavior, and substance addiction.

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Intramolecular reaction of 2-tropylio-3-(5-substituted 2-furyl) benzothiophenes (3), prepared from the corresponding 2-cycloheptatrienyl-3-(5- substituted 2-furyl)benzothiophenes (2), afforded the beta-(azuleno[1,2-b] benzothienyl)-alpha,beta-unsaturated ketones (4), which are otherwise difficult to obtain, in moderate yields. The reaction involves a ring-opening process of the furan ring by intramolecular attack of the tropylium ion onto the 2-position of the furan ring. Similarly, beta-(azuleno[2,1-b]benzothienyl)- alpha,beta-unsaturated ketones (8) were obtained from the corresponding 3-tropylio-2-(5-substituted 2-furyl)benzothiophenes (7) albeit in lower yields. The molecular and crystal structures of the methyl ketone derivative, 8a, are discussed on the basis of X-ray structure analysis.

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Metal catalyst and ligand design,
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Synthesis of 1-, 2-, 3- and 4-fluorobenzophenanthrenes by photocyclization of appropriate beta-naphth-1-yl fluorostyrene is described.An improved synthesis of 6-fluorobenzophenanthrene was developed.Partial photochemical debromination occured upon cyclization of 2-bromo-7-fluoro-benzophenanthrene.

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Metal catalyst and ligand design,
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The present invention discloses compounds of formula I, or pharmaceutically acceptable salts, esters, or prodrugs thereof: Formule (I) which exhibit antibacterial properties. The present invention further relates to pharmaceutical compositions comprising the aforementioned compounds for administration to a subject in need of antibiotic treatment. The invention also relates to methods of treating a bacterial infection in a subject by administering a pharmaceutical composition comprising the compounds of the present invention. The invention further includes process by which to make the compounds of the present invention.

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Metal catalyst and ligand design,
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Benzyl triphenyl phosphonium bromide (BTPPB) has been evaluated as a corrosion inhibitor for mild steel in aerated 0.5 M sulfuric acid solution by galvanostatic polarization and potentiostatic polarization methods. The effect of BTPPB on the corrosion current is measured at various temperatures and concentrations. The inhibitor efficiencies, effective activation energies and heat of adsorption have been calculated. The inhibition efficiency increases with increase in inhibitor concentration to reach 99.3% for 10-2 M. The nature of adsorption of BTPPB on the metal surface has also been examined. Probable mode of adsorption on the metal surface has been proposed using infrared spectroscopic studies. The electrochemical results have also been supplemented by surface morphological studies and quantum chemical analysis.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI