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Background: The reaction of aryl halides or vinyl halides with activated alkenes in the presence of Palladium-catalyst along with a base for the formation of the C-C bond is called the Heck reaction. This reaction has been employed extensively in the synthesis of heterocyclic compounds. Methodology: We have highlighted these applications in 2010. Conclusion: This review aims to cover the recent application of the Heck reaction in the synthesis of heterocyclic compounds during a period from 2010 to 2017. Dedicated to my dearest ? TEEDA? on the occasion of her third birthday.

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The present invention relates to a use of a cyclic imidate as a ligand for catalysis in which the ligand contains sub-structure (Y) as a minimal structural motive, wherein the carbon atoms and the nitrogen atom can be optionally substituted by a chemical substituent.

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Organometallic compounds of platinum containing ortho metalated para-nitro-benzamidate or 1-naphthalene-methylamine have been prepared by one-pot synthesis. The para-nitro-benzamidate [Pt{K2C,N-pNO2-C6H4C(O)NH}(R,R-DACH)] (compound 2) was obtained starting from [PtCl2(R,R-DACH)] and para-nitro-benzonitrile, which, in the reaction conditions, hydrolyzes to the corresponding amide and forms the dinuclear intermediate [Pt2{mu-N,O-pNO2-C6H4C(O)NH}2(R,R-DACH)2]SO4 (compound 1·SO4) with HH or HT arrangement of the two bridging amidato ligands. Compound 1·SO4, kept at 90 C for few hours, transforms into 2. The ortho-metalated PtII derivative with 1-naphthalene-methylamine [PtCl{K2C,N-C10H6CH2NH2}(DMSO)] (3) was obtained by direct reaction of [PtCl2(DMSO)2] with the amine. Unlike compound 2 that has no labile ligands, compound 3 has Cl and DMSO ligands that can be released, allowing the formation of cross-links with DNA. Oxidation of 3 to the PtIV counterpart was performed with PhICl2 (compound 4). Unexpectedly, although six-coordinate complexes of PtIV are considered to be inert, 4 underwent spontaneous isomerization from the mer to the fac isomer. All compounds have been fully characterized by multinuclear NMR spectroscopy, which has enabled complete assignment of all proton resonances. In the case of compound 2, a single-crystal X-ray investigation was also performed, showing, with the only exception of the puckered cyclohexane ring, a complete planarity of the complex frame, which could favor an intercalative interaction with DNA.

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Can You Really Do Chemisty Experiments About (1R,2R)-Cyclohexane-1,2-diamine

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Stereoisomers, trans-RR, trans-SS, and cis forms, of N,N?-bis- (phenanthrolin-2-yl)-1,2-cyclohexanediamine conjugates were prepared, and their DNA binding activity was evaluated. The copper complexes of the conjugates (ligand:Cu(II) = 1:1 and 1:2) cleave DNA in the same order of the DNA binding activity of the conjugates, trans-RR > cis > trans-SS.

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We report a new thiourea – Bronsted acid cooperative catalytic system for the enantioselective cyanosilylation of aldehydes with yields up to 90% and enantioselectivities up to 88%. The addition of an achiral acid was found to be crucial for high asymmetric induction. Mechanistic investigations using a combination of NMR, ESI-MS, and density functional theory computations (including solvent corrections) at the M06/6-31G(d,p) level of theory suggest that the key catalytic species results from the cooperative interaction of bifunctional thioureas and an achiral acid that form well-defined chiral hydrogen-bonding environments.

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An efficient kinetic resolution of primary propargylic amines with s-factors of up to 56 is reported. The strategy is based on a dual catalytic approach, namely the use of a newly developed and easy-to-make thiourea-amide anion binding catalyst in combination with 4-(dimethylamino)pyridine (DMAP), both employed at a 5 mol % catalyst loading. Benzylic amines are also resolved with s-factors of up to 38.

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Condensation of the O-protected hydroxyferrocene carbaldehyde (Sp)-1 with suitable diamines, followed by liberation of the hydroxyferrocene moiety leads to a new type of ferrocene-based salen ligands (3). While the use of ethylenediamine in the condensation reaction yields the planar-chiral ethylene-bridged ligand [(Sp,Sp)-3a], reaction with the enantiomers of trans-1,2-cyclohexylendiamine gives rise to the corresponding diastereomeric cyclohexylene-bridged systems [(S,S,Sp,Sp)-3b and (R,R,Sp,Sp)-3c], which feature a combination of a planar-chiral ferrocene unit with a centrochiral diamine backbone. Starting with the ferrocene-aldehyde derivative (Rp)-1, the enantiomeric ligand series (3d/e/f) is accessible via the same synthetic route. The (Sp)-series of these newly developed N2O2-type ligands was used for the construction of the corresponding mononuclear bis(isopropoxy)titanium (4a/b/c), methylaluminum (5a/b/c) and chloroaluminum-complexes (6a/b/c), which were isolated in good yields and identified by X-ray diffraction in several cases. The aluminum complexes (5/6) were successfully used in the Lewis-acid catalyzed addition of trimethylsilylcyanide to benzaldehyde, yielding the corresponding cyanohydrins in 45-62% enantiomeric excess.

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A new macrocyclic NADH model 1 has been designed and synthesised. The new model consists of the same subunits as previously reported models. However, the present model is designed as such that the pyridine nitrogen of the nicotinamide units are not incorporated in the macrocyclic framework. Thus, properties such as solubility can easily be varied by alkylation with an appropriate agent. The macrocyclic framework was prepared in 7 steps. Methylation of the pyridine nitrogens followed by reduction gave the desired model. This model compound was found to reduce methyl benzoylformate stereoselectively in good yield with 48% enantiomeric excess.

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Schiff bases derived from (1R,2R)-1,2-diaminocyclohexane and 1 eq. of salycylic (or substituted salycylic) aldehyde form stereochemically inert positively charged chiral octahedral Co iii complexes of Delta-configuration with the stereoselectivity approaching 100%. To evaluate the calatylic activity and stereoinduction of the resulting complexes with various counteranions in the outer sphere, a model reaction of trimethylsilyl cyanide addition to benzaldehyde was used. O-trimethylsilylmandelonitrile formed in the process had an enantiomeric purity up to 27%. Complexes with F – counterion showed high catalytic activity.

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A procedure is described for the automated screening and lead optimization of a supramolecular-ligand library for the rhodium-catalyzed asymmetric hydrogenation of five challenging substrates relevant to industry. Each catalyst is (self-) assembled from two urea-functionalized ligands and a transition-metal center through hydrogen-bonding interactions. The modular ligand structure consists of three distinctive fragments: the urea binding motif, the spacer, and the ligand backbone, which carries the phosphorus donor atom. The building blocks for the ligand synthesis are widely available on a commercial basis, thus ena-bling access to a large number of ligands of high structural diversity. The simple synthetic steps enabled the scale-up of the ligand synthesis to multigram quantities. For the catalyst screening, a library of twelve new chiral ligands was prepared that comprised substantial variation in electronic and steric properties. The automated procedures employed ensured the fast catalyst assembly, screening, and direct acquisition of samples for analysis. It appeared that the most selective catalyst was different for every substrate investigated and that small variations in the building blocks had a major impact on the catalyst performance. For two substrates, a catalyst was found that provided the product with outstanding enantioselectivity. The subsequent automated optimization of these two leads showed that an increase of catalyst loading, dihydrogen pressure, and temperature had a positive effect on the catalyst activity without affecting the catalyst selectivity.

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Metal catalyst and ligand design,
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