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Sulfination by using Pd-PEPPSI complexes: Studies into precatalyst activation, cationic and solvent effects and the role of butoxide base

The activation of PEPPSI precatalysts has been systematically studied in Pd-catalysed sulfination. Under the reactions conditions of the sulfide and KOtBu in toluene, the first thing that happens is exchange of the two chlorides on the PEPPSI precatalyst with the corresponding sulfides, creating the first resting state; it is via this complex that all Pd enters the catalytic cycle. However, it is also from this same complex that a tri-Pd complex forms, which is a more persistent resting state. Under standard reaction conditions, this complex is catalytically inactive. However, if additional pyridine or a smaller base (i.e., KOEt) is added, this complex is broken down, presumably initially back to the first resting state and it is again capable of entering the catalytic cycle and completing the sulfination. Of note, once the tri-Pd complex forms, one equivalent of Pd is lost to the transformation. Related to this, the nature of the cation of the sulfide salt and solvent dielectric is very important to the success of this transformation. That is, the less soluble the salt the better the performance, which can be attributed to lowering sulfide concentration to avoid the movement of the Pd-NHC complex into the above described off-cycle sulfinated resting states.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

Top Picks: new discover of 2,4-Dimethylpyridine

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Nitric oxide synthase inhibitors that interact with both heme propionate and tetrahydrobiopterin show high isoform selectivity

Overproduction of NO by nNOS is implicated in the pathogenesis of diverse neuronal disorders. Since NO signaling is involved in diverse physiological functions, selective inhibition of nNOS over other isoforms is essential to minimize side effects. A series of alpha-amino functionalized aminopyridine derivatives (3-8) were designed to probe the structure-activity relationship between ligand, heme propionate, and H4B. Compound 8R was identified as the most potent and selective molecule of this study, exhibiting a K i of 24 nM for nNOS, with 273-fold and 2822-fold selectivity against iNOS and eNOS, respectively. Although crystal structures of 8R complexed with nNOS and eNOS revealed a similar binding mode, the selectivity stems from the distinct electrostatic environments in two isoforms that result in much lower inhibitor binding free energy in nNOS than in eNOS. These findings provide a basis for further development of simple, but even more selective and potent, nNOS inhibitors.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

Discovery of (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol

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HIV-1 protease inhibitors with a transition-state mimic comprising a tertiary alcohol: Improved antiviral activity in cells

By a small modification in the core structure of the previously reported series of HIV-1 protease inhibitors that encompasses a tertiary alcohol as part of the transition-state mimicking scaffold, up to 56 times more potent compounds were obtained exhibiting EC50 values down to 3 nM. Three of the inhibitors also displayed excellent activity against selected resistant isolates of HIV-1. The synthesis of 25 new and optically pure HIV-1 protease inhibitors is reported, along with methods for elongation of the inhibitor P1? side chain using microwave-accelerated, palladium-catalyzed cross-coupling reactions, the biological evaluation, and X-ray data obtained from one of the most potent analogues cocrystallized with both the wild type and the L63P, V82T, I84 V mutant of the HIV-1 protease.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

Extracurricular laboratory:new discovery of (1S,2R)-1-Amino-2,3-dihydro-1H-inden-2-ol

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Enantioselective access to bicyclo[4.2.0]octanes by a sequence of [2+2] photocycloaddition/reduction/fragmentation

Tricks of the trade: Because intramolecular Cu-catalyzed access to bicyclo[4.2.0]octanes is not feasible, an oxygen bridge was introduced to facilitate the [2+2] photocycloaddition. Starting from compounds similar to 1, products such as 2 could be obtained enantioselectiviely in three steps after ring-opening metathesis (see scheme). Copyright

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Reference of 126456-43-7, Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps.In a article, 126456-43-7, molcular formula is C9H11NO, introducing its new discovery.

On the way to biodegradable poly(hydroxy butyrate) from propylene oxide and carbon monoxide via beta-butyrolactone: Multisite catalysis with newly designed chiral indole-imino chromium(III) complexes

Enantioenriched poly(hydroxy butyrate) (PHB) is a biodegradable polyester of significant commercial interest as an environmentally benign substitute of commodity polyolefines. We report on the design and development of new chiral indole-based ligand families and on their chromium(III) complexes as enantioselective catalysts for the conversion of propylene oxide and carbon monoxide to enantioenriched beta-butyrolactone, the key monomer for the production of PHB by ring-opening polymerization. The enantioselective carbonylation catalysts are based on new chiral tri- and tetradentate [N2O] and [N4] chromium(III) complexes containing chiral indolaldimine ligand scaffolds. The conceptual design of these ligands is inspired by Jacobsen’s salicylaldimine lead structure; the key difference is an exchange of the salicyl-O-donor against an indole-N-donor, allowing additional structural diversity and stereoelectronic tuning by the indole substitution pattern. Synthetically, chiral indolealdimines are easily accessible from 7-formylindoles by standard Schiff base condensation with chiral amine building blocks; the 7-formylindoles in turn are synthesized from the corresponding 7-bromoindoles by the Rapoport synthesis, and the starting 7-bromoindoles are accessible from 2-bromoaniline by the classical Fischer indole synthesis. Three generations of chiral [N2O] and [N4] chromium(III) catalysts have been developed and evaluated in the enantioselective carbonylation of racemic propylene oxide with carbon monoxide using tetracarbonylcobaltate as the nucleophilic reagent for the insertion of carbon monoxide into the activated propylene oxide/chiral Lewis acid complex. The best catalyst out of 10 candidates showed at a temperature of 80 C an activity of 37% conversion, 100% chemoselectivity, and 19% stereoselectivity.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Reactions of 2,3-diferrocenylcyclopropenilium salts with bis-1,4-N,O-nucleophiles: Novel synthesis, characterization, chemical and electrochemical properties of the 2-(Z-1,2-diferrocenylvinyl)- 4,5-dihydrooxazole derivatives

A new method of synthesis of 2-(Z-1,2-diferrocenylvinyl)-4,5-dihydrooxazoles 3a-f and 5, 2-(Z-1,2-diferrocenylvinyl)-4,5-dihydrooxazol-3-ium salts 4a-f, 4g,h, and 9h-j by reactions of 2,3-diferrocenylcyclopropenylium salts 1a,b with 1,2-amino- and 1,2-N-alkylaminoalcohols in the presence of Et3N is described. The interactions of the salts 4a,d,f and 9h-j with morpholine and piperidine results in the corresponding (E)-2-[(N-2?,3?-diferrocenylacryloyl-2-(N-alkyl)amino]ethylmorpholines and piperidines. The characterization of the new compounds was done by IR, 1H and 13C NMR spectroscopy, mass-spectrometry, elemental analysis, and X-ray diffraction studies. Electrochemical properties of the compounds 3a-d and 4a-d were investigated using cyclic square voltammetry. One adsorption process and two electrochemical processes II and III, attributed to the oxidations of the ferrocene moieties, E0?(II), E0?(III), and comproportionation constant Kcom are reported.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Thiourea catalyzed organocatalytic enantioselective Michael addition of diphenyl phosphite to nitroalkenes

Bifunctional thiourea catalyzes the enantioselective Michael addition reaction of diphenyl phosphite to nitroalkenes. This methodology provides a facile access to enantiomerically enriched beta-nitrophosphonates, precursors for the preparation of synthetically and biologically useful beta-aminophosphonic acids. DFT level of computational calculations invoke the attack of the diphenyl phosphite to the nitroolefin by the Re face, this give light to this scarcely explored process update in the literature. The computational calculations support the absolute configuration obtained in the final adducts.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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The impact of pressure and frictional heating on retention, selectivity and efficiency in ultra-high-pressure liquid chromatography

The effects of pressure and frictional heating deserve serious consideration in ultra-high-pressure liquid chromatography (UHPLC) separations, as the pressures used can be three times greater than those in conventional high-performance LC (HPLC). We show that the effects of pressure alone can give useful selectivity effects, especially when separating molecules of different size. Frictional heating effects can cause serious losses in column efficiency and may also give changes in the selectivity of the separation. Nevertheless, the detrimental effect of frictional heating can be reduced, for instance by the judicious selection of column thermostat and particle type. In practical situations, pressure and heating effects occur simultaneously and can cause problems in transferring methods from conventional HPLC to UHPLC. In reversed-phase separations, the typical effect of increased retention with increasing pressure is counteracted by the reduction in retention that usually occurs at elevated temperatures.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Kinetic resolution of amino alcohol derivatives with a chiral nucleophilic catalyst: Access to enantiopure cyclic cis-amino alcohols

Acylative kinetic resolution of racemic cyclic cis-amino alcohol derivatives with a chiral nucleophilic catalyst proceeds enantioselectively (s = 10-21) at ambient temperature to give enantiopure recovered materials, and the % conversion of the acylation can be readily controlled by the amount of acid anhydride.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis

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Novel HIV reverse transcriptase inhibitors

The invention is related to compounds of Formula (I), (II), or (III): or a pharmaceutically acceptable salt, solvate, ester, and/or phosphonate thereof, compositions containing such compounds, and therapeutic methods that include the administration of such compounds.

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Reference£º
Chiral nitrogen ligands in late transition metal-catalysed asymmetric synthesis¡ªI. Addressing the problem of ligand lability in rhodium-catalysed hydrosilations,
Nitrogen-Containing Ligands for Asymmetric Homogeneous and Heterogeneous Catalysis