Our Top Choice Compound: C9H11NO

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A new class of organocatalyst has been developed that incorporates a sulfinyl group as a urea or thiourea substituent. The sulfinyl group serves to simultaneously acidify the urea and provide asymmetric induction in hydrogen-bond-catalyzed reactions. The utility of this new catalyst structure is demonstrated by the high selectivity provided in the aza-Henry reaction not only for aromatic N-Boc imine substrates but also for aliphatic imines for which enantioselective H-bonding catalysis has not previously been demonstrated. Copyright

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

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Ionic liquid solvents N-hexylpyridinium bistrifylimide ([C 6pyr][Tf2N]] and 1-butyl-3-methylimidazolium hexafluorophosphate ([C4mim][PF6]) promoted the displacement of anionic ligands by pyridine derivatives in trans-(Ph 3P)2Rh(CO)NO3 to a much greater extent than did dichloromethane. Thus, addition of a slight excess of 2-fluoropyridine to trans-(Ph3P)2Rh(CO)NO3 in [C 4mim][PF6] gave a 29:71 product mixture of trans-(Ph 3P)2Rh(CO)NO3:[trans-(Ph3P) 2Rh(CO)(2-fluoropyridine)][NO3], while the ratio was 91:9 in dichloromethane.

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

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The title heteroleptic neutral cobalt(II) tri-tert-butoxysilanethiolate complexes with monodentate nitrogen bases (L) as additional ligands have been prepared by the reactions of [Co{mu-SSi(OtBu)3}{SSi(OtBu) 3}(NH3)]2 (1) with respective bases. For pyridine both types have been prepared – with two (2) or one (3) nitrogen ligand bonded to cobalt(II). [Co{SSi(OtBu)3}2(L)] complexes have been obtained also with 2-picoline (5), 2,4-lutidine (6), 3,5-lutidine (7), and [Co{SSi(OtBu)3}2(L)2] also with N-methylimidazole (8) and morpholine (9). Molecular and crystal structures of the six compounds have been determined by single-crystal X-ray structural analysis. In 3, 5 and 7 three-coordinated cobalt(II) seems to interact very weakly with two oxygen atoms from two Si(OtBu)3 moieties approaching highly distorted trigonal bipyramidal geometry. Compounds 2, 8 and 9 have distorted tetrahedral structures. Both types of complexes gave characteristic electronic spectra, similar within each type.

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

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The heterogeneous-catalytic synthesis of pyridine bases from dimethylethynylcarbinol and ammonia in the presence of acetaldehyde and also of monoethanolamine was investigated.The employed zinc-chromium-aluminum catalyst was prepared from the respective compounds by the suspension method.The effect of temperature and of the initial reagents on the formation of alkylpyridines was studied.Possible hypothetical reactions were investigated, and their schemes were demonstrated by alternative synthesis.

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

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A method for producing a polydiene, the method comprising of combining a lanthanide compound, an alkylating agent, a halogen source, and optionally conjugated diene monomer to form an active preformed catalyst; independent of step (i), introducing an amine with conjugated diene monomer to be polymerized; independent of step (i), introducing the active preformed catalyst to the conjugated diene monomer to be polymerized to form an active polymerization mixture, where the active polymerization mixture includes less than 10% by weight, based on the total weight of the active polymerization mixture, of a solvent; and allowing the monomer to be polymerized to polymerize in the presence of the amine.

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

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The carbocyclization of non-conjugated dienes mediated by organometallics is an important reaction for the synthesis of a variety of carbocyclic derivatives, but the direct annulation of dienes with an inert C?H bond of a substrate has remained unexplored to date. We herein report a series of novel rare-earth dialkyl complexes bearing a phosphinoamide anion and demonstrate that the combination of a mono(phosphinoamido)-ligated scandium dialkyl complex with B(C6F5)3 results in an excellent catalyst for the cis-selective cyclization of 1,5-dienes with the ortho-C(sp2)?H bond of pyridines to afford a new family of pyridyl-functionalized 1,3-disubstituted cyclopentane derivatives containing monocyclic, bicyclic, spirocyclic, and heterocyclic skeletons in moderate to excellent yields with high diastereoselectivities (cis/trans up to 99:1).

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

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In the present work, for the first time a new set-up was presented for simultaneous extraction of acidic and basic drugs using a recent novel electrically-enhanced microextraction technique, termed electromembrane extraction at low voltages followed by high performance liquid chromatography with ultraviolet detection. Nalmefene (NAL) as a basic drug and diclofenac (DIC) as an acidic drug were extracted from 24mL aqueous sample solutions at neutral pH into 10muL of each acidified (HCl 50mM) and basic (NaOH 50mM) acceptor solution, respectively. Supported liquid membranes including 2-nitrophenyl octyl ether containing 5% di-(2-ethylhexyl) phosphate and 1-octanol were used to ensure efficient extraction of NAL and DIC, respectively. Low voltage of 40V was applied over the SLMs during 14min extraction time. The influences of fundamental parameters affecting the transport of target drugs were optimized using experimental design. Under optimal conditions, NAL and DIC were extracted with extraction recoveries of 12.5 and 14.6, respectively, which corresponded to preconcentration factors of 300 and 350, respectively. The proposed technique provided good linearity with correlation coefficient values higher than 0.9956 over a concentration range of 8-500mugL-1 and 12-500mugL-1 for NAL and DIC, respectively. Limits of detection and quantifications, and intra-day precisions (n=3) were less than 4mugL-1, 12mugL-1, and 10.1%, respectively. Extraction and determination of NAL and DIC in human urine samples were successfully performed. In light of the data obtained in the present work, this new set-up for EME with low voltages has a future potential as a simple, selective, and fast sample preparation technique for simultaneous extraction and determination of acidic and basic drugs in different complicated matrices.

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

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Spermidine alkaloids are polyaminated macrocycles containing a lactam ring, which are biosynthetically derived from L-Orn or L-Arg via putrescine intermediates. The presence of these polyamines in nature is very limited, occurring in only a few plant families, and therefore the isolation of spermidine alkaloids serves chemotaxonomic purposes. The interest in the isolation and synthesis of these alkaloids also results from the structural complexity and broad range of bioactivity attributed to these macrocyclic structures. In recent years, several research groups have been dedicated to these triaminated compounds and previously unknown natural products, or already described structures in new plant species, with potential biological applications have been reported. Novel synthetic strategies and the application of more recent synthetic methodologies have allowed new perspectives for the development of new bioactive molecules. The latest progress on the isolation, identification, biological activity, and chemical synthesis of spermidine alkaloids is summarized in this review.

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

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The synthesis of new chiral auxiliaries, 7-alkyl substituted cis-1-amino-2-indanol derivatives, was established by the Diels-Alder reaction of 1-substituted dienes with cyclopentenone followed by the asymmetric epoxidation of the resulting indene derivatives and then the Ritter reaction. These bulky cis-aminoindanol derivatives are very effective as chiral auxiliaries and nitrogen sources in the asymmetric 6pi-azaelectrocyclization. The corresponding 4-alkyl derivative was also prepared using a similar method.

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

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This paper presents the enantioseparation using glucose, cellobiose, lactose and raffinose as chiral selector bonded to silica gel via an arm in HPLC. Surprisingly, they also possess high enantioseparation selectivity, may be used in normal-phase and reversed-phase mode, and there is a big chiral discriminating complementary. This work indicates that oligosaccharides could soon become very attractive as a new class of chiral stationary phase for HPLC.

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