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Serine proteases play key roles in many biological processes and are associated with several human diseases such as thrombosis or cancer. During the search for selective inhibitors of serine proteases, a family of linear peptides named the aeruginosins was discovered in marine cyanobacteria. We herein report an entry route into the synthetically challenging core fragment of these natural products. Starting from the common oxabicyclic building block 11, we accessed the octahydroindole core of the aeruginosins, exemplified by the total synthesis of microcin SF608 (2). Key to the synthetic strategy is a highly efficient nucleophilic opening of an oxabicyclo[2.2.1]heptane producing the hydroindole motif of microcin SF608. Moreover, during the synthetic efforts we have observed an unusual regioselective epoxide reduction. Detailed experimental studies of this reaction led us to propose a mechanistic rationale involving intramolecular hydrogen atom delivery by a carbamate NH group to control the regioselectivity of the homolytic epoxide cleavage. Expect the unexpected! An entry route to the aeruginosin protease inhibitors is reported and showcased on the total synthesis of microcin SF608 (see scheme). Detailed experimental studies of an unusual regioselective epoxide reduction observed during this synthesis suggests a mechanistic rationale for this transformation involving intramolecular hydrogen atom delivery by a carbamate NH to direct the regioselectivity of the homolytic epoxide cleavage.

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Reference:
Chiral Catalysts,
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The reaction of Ni(COD)2, IPr, and nitrile affords dimeric [Ni(IPr)RCN]2 in high yields. X-ray analysis revealed these species display simultaneous eta1- and eta2-nitrile binding modes. These dimers are catalytically competent in the formation of pyridines from the cycloaddition of diynes and nitriles. Kinetic analysis showed the reaction to be first order in [Ni(IPr)RCN]2, zeroth order in added IPr, zeroth order in nitrile, and zeroth order in diyne. Extensive stoichiometric competition studies were performed, and selective incorporation of the exogenous, not dimer bound, nitrile was observed. Post cycloaddition, the dimeric state was found to be largely preserved. Nitrile and ligand exchange experiments were performed and found to be inoperative in the catalytic cycle. These observations suggest a mechanism whereby the catalyst is activated by partial dimer-opening followed by binding of exogenous nitrile and subsequent oxidative heterocoupling.

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Reference:
Chiral Catalysts,
Chiral catalysts – SlideShare

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A series of imidazolium salts with various N-aryl groups were synthesized, and their catalytic activities were evaluated to investigate the contribution of the N-aryl groups to the catalytic activity in the synthesis of gamma-butyrolactone through an a3?d3-umpolung addition. Imidazolylidenes with 2,6-diethylphenyl groups were effective catalysts, and several mechanistic studies, including a deuterium kinetic isotope effect study, revealed that both steric and kinetic effects were responsible for the enhanced catalytic activity.

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In an article, published in an article, once mentioned the application of 250285-32-6, Name is 1,3-Bis(2,6-diisopropylphenyl)imidazolium chloride,molecular formula is C27H37ClN2, is a conventional compound. this article was the specific content is as follows.HPLC of Formula: C27H37ClN2

Reaction of N-heterocyclic carbene iron(0) tetracarbonyl complexes with hydrosilanes (triphenylsilane, methyldiphenylsilane and diphenylsilane) under UV irradiation (350 nm) afforded the octahedral N-heterocyclic carbene iron(II) silyl hydride complexes in yields up to 95 %, resulting from the oxidative addition of the hydrosilane. Eight iron silyl hydrides were obtained and characterized by NMR and X-ray diffraction analysis. Noticeably, the geometry of the iron-hydride complexes and the bent structures of the carbonyl ligands were rationalized by DFT calculations.

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Reference:
Chiral Catalysts,
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In an article, published in an article, once mentioned the application of 250285-32-6, Name is 1,3-Bis(2,6-diisopropylphenyl)imidazolium chloride,molecular formula is C27H37ClN2, is a conventional compound. this article was the specific content is as follows.Computed Properties of C27H37ClN2

Boryl halide, carboxylate and sulfonate complexes of 1,3-bis(2,6- diisopropylphenyl)imidazol-2-ylidene (dipp-Imd-BH2X, X = halide or sulfonate) have been prepared from the parent borane dipp-Imd-BH3 by (1) substitution reactions with R-X (X = halide or sulfonate), (2) reactions with electrophiles (like I2 or NIS), or (3) acid/base reactions with HX (provided that HX has a pKa of about 2 or less). Dipp-Imd-BH 2I is most conveniently prepared by reaction with diiodine while dipp-Imd-BH2OTf is best prepared by reaction with triflic acid. These and other less reactive complexes behave as electrophiles and can be substituted by a wide range of heteroatom nucleophiles including halides, thiolates and other sulfur-based nucleophiles, isocyanate, azide, nitrite, and cyanide. The resulting products are remarkably stable, and many have been characterized by X-ray crystallography. Several are members of very rare classes of functionalized boron compounds (boron azide, nitro compound, nitrous ester, etc.).

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A copper catalyst generated in situ from widely available copper salt and imidazolium salt in the presence of t-BuOK showed high efficiency for the semihydrogenation of a wide range of internal and terminal alkynes to their corresponding alkenes without obvious over-reduction. Functional groups, such as hydroxyl, nitro, halides, and amino, etc. were tolerated. The Z/E ratios of the obtained alkenes were generally >99%. Finally, semireduction of bulky alkynes also went smoothly.

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Chiral Catalysts,
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Soft reaction conditions, particularly important in total synthesis, have dragged many researchers into the field of silylated organic compounds. Hereby, we describe a new copper-catalyzed vinylsilane transformation. Various vinylsilanes were allylated by using a copper(I) salt, and this led to the formation of polysubstituted 1,4-dienes bearing sensitive moieties such as halogens, ketones, and aldehydes. Hereby is described a new copper-catalyzed vinylsilane transformation. Various vinylsilanes were allylated by using copper(I) salts, and this led to the formation of polysubstituted 1,4-dienes bearing sensitive moieties such as halogens, ketones, and aldehydes. TBAT = tetrabutylammonium difluorotriphenylsilicate. Copyright

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A novel platinum complex with 1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidenyl ligand has been synthesized and characterized on the basis of elemental analysis, MS, 1H and 13C NMR spectroscopy, X-ray Absorption Spectroscopy and single crystal X-ray diffraction studies. The XRD determination of the complex (monoclinic, C2/c) revealed a structure in which the platinum (II) centre coordinates two chlorides, a carbon atom of the N-heterocyclic carbene (NHC) and is stabilized by coordinating the nitrogen atom of a 3-chloropyridine molecule, forming an over-all square planar geometry. By prolonging the time of the reaction, it was possible to obtain the trans-dichloridobis(3-chloropyridine) platinum(II) complex under the same reaction conditions. The electronic and molecular properties of both complexes were investigated and compared by means of Near Edge X-ray Absorption Fine Structure spectroscopy (NEXAFS), supported by numerical simulations. The platinum carbene complex obtained was tested in a series of C-H activation and hydrosilylation reactions.

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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.250285-32-6, Name is 1,3-Bis(2,6-diisopropylphenyl)imidazolium chloride, molecular formula is C27H37ClN2. In a Article,once mentioned of 250285-32-6, Formula: C27H37ClN2

Cinchona alkaloids were used as Lewis base catalysts in the title reaction. The [4+2] cyclization of alpha,beta-unsaturated acyl chlorides with electron-deficient alkenes derived from oxindole gave the corresponding spirocarbocyclic oxindoles. Copyright

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Chiral Catalysts,
Chiral catalysts – SlideShare

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A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 250285-32-6, Name is 1,3-Bis(2,6-diisopropylphenyl)imidazolium chloride, molecular formula is C27H37ClN2. In a Article,once mentioned of 250285-32-6, name: 1,3-Bis(2,6-diisopropylphenyl)imidazolium chloride

Based on the synthesis of two new hexa-coordinate N-heterocyclic carbene (NHC) substituted precursors FeI2(CO)3(NHC) with NHC = IPr (1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) (2) and NHC = SIPr (1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylide) (3) and two known complexes FeI2(CO)3SIMes, SIMes = (1,3-bis(2,4,6-trimethylphenyl)-imidazol-2-ylide) (1) and FeI2(CO)3IMe IMe = 1,3-bismethylimidazol-2-ylidene (4), four new mononuclear [Fe]-hydrogenase model complexes Fe(CO)2(NS)(NHC) (NS = aminothiophenol; 5, NHC = SIMes; 6, NHC = IPr; 7, NHC = SIPr; 8, NHC = IMe) were prepared by substitution of two iodine ligands with the help of dipotassium-aminothiophenol salt and subsequently the absence of a CO ligand. New complexes 2, 3 and 5-8 were fully structurally characterized by infrared spectroscopy (IR), elemental analysis, NMR spectroscopy, and X-ray crystallography. IR spectroscopy studies show that complexes 5-8 exhibit similar IR patterns and absorption wavelengths in terms of nu(CO) with the active site of [Fe]-hydrogenase. The facile protonation/deprotonation of the NS ligand of complexes 6 and 7 was disclosed with the assistance of IR spectroscopy. The NS ligand accepts a proton reversibly as an internal base, generating two protonated species, [Fe(CO)2IPr(H-NS)]+ and [Fe(CO)2SIPr(H-NS)]+, which play the same role with the intrinsic cysteine thiolate ligand in [Fe]-hydrogenase. DFT results showed that the N atom of the NS ligand is the thermodynamically active proton acceptor in acetone while the NS ligand is prone to be dually protonated first in the N atom and then the S atom in the gas phase. Complex 5 exhibited simultaneous protonation and the combination of CO, forming a new mer-tricarbonyl species in the presence of CO and HBF4. It showed easy reversible deprotonation and deprivation of CO with the assistance of t-BuOK or Et3N. Also, the electrochemical properties of these new pentacoordinate model complexes were explored through cyclic voltammetry, which enabled us to identify the contributions of different NHC ligands to the complexes’ redox properties.

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Reference:
Chiral Catalysts,
Chiral catalysts – SlideShare