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Catalytic asymmetric synthesis of spirocyclic azlactones by a double Michael-addition approach

Spirocyclic azlactones are shown to be useful precursors of cyclic quaternary amino acids, such as the constrained cyclohexane analogues of phenylalanine. These compounds are of interest as building blocks for the synthesis of artificial peptide analogues with controlled folds in the peptide backbone. They were prepared in the present study by a step- and atom-economic catalytic asymmetric tandem approach, requiring two steps starting from N-benzoyl glycine and divinylketones. The key of this protocol is the enantioselective formation of the azlactone spirocycles, which involves a PdII-catalyzed double 1,4-addition of an in situ generated azlactone intermediate to the dienone (a formal [5+1] cycloaddition). As the catalyst, a planar chiral ferrocene bispalladacycle was used. Mechanistic studies suggest a monometallic reaction pathway. Although the diastereoselectivity was found to be moderate, the enantioselectivity is usually high for the formation of the azlactone spirocycles, which contain up to three contiguous stereocenters. Spectroscopic studies have shown that the spirocycles often prefer a twist over a chair conformation of the cyclohexanone moiety. A formal [5+1] cycloaddition of divinylketones and an in situ-generated glycine-derived azlactone was catalyzed by a chiral bis-palladacycle and provided highly enantioenriched, spirocyclic, masked amino acid products. The latter were used to synthesize biologically interesting constrained cyclohexane analogues of phenylalanine in just two steps (see scheme). Copyright

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Highly enantioselective synthesis of spiro[cyclohexanone-oxindoles] and spiro[cyclohexanone-pyrazolones] by asymmetric cascade [5+1] double Michael reactions

The asymmetric catalytic synthesis of naturally occurring and biologically active spiro compounds is a challenge for modern chemical methodology. Here we report the construction of spiro compounds through cascade [5+1] double Michael reactions between divinyl ketones and N-unprotectedoxindoles or N-phenyl-protected pyrazolones catalyzed by a combination of the easily available 9-amino-9-deoxy-epi-quinine with N-Boc-D-phenylglycine. The desired multistereogenic spiro[cyclohexanone-oxindoles and -pyrazolones] were obtained with high yields (up to 98 %) andstereoselectivities (up to >20:1 dr, 99 % ee). An efficient approach to spiro compounds through cascade [5+1] double Michael reactions between divinyl ketones and oxindoles or N-protected pyrazolones in the presence of 9-amino-9-deoxy-epi-quinine and N-Boc-D-phenylglycine is reported. Multistereogenic spiro[cyclohexanone- oxindoles and -pyrazolones] are obtained with high yields (up to 98 %) and stereoselectivities (up to >20:1 dr, 99 % ee). Copyright

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Reaction of 1,5-diarylpenta-1,4-dien-3-ones with methyl 1-bromocycloalkanecarboxylates and zinc

Methyl 1-bromocyclopentane-, 1-bromocyclohexane- and 1- bromocycloheptanecarboxylates react with zinc and 1,5-diarylpenta-1,4-dien-3- ones to form 10-aryl-8-(2-arylethenyl)-7-oxaspiro[4.5]dec-8-en-6- ones, 5-aryl-3-(2-arylethenyl)-2-oxaspiro[5.5]undec-3-en-1-ones, and 5-aryl-3-(2-arylethenyl)-2-oxaspiro[5.6]- dodec-3-en-1-ones, respectively. Pleiades Publishing, Ltd., 2011.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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A highly organocatalytic stereoselective double Michael reaction: Efficient construction of optically enriched spirocyclic oxindoles

An effective double Michael reaction has been disclosed to access spirocyclic oxindoles in high yields (up to 98%) and excellent enantioselectivities (up to 98% ee).

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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An efficient catalyst free synthesis of nitrogen containing spiro heterocycles via [5 + 1] double Michael addition reaction

2,4-Diazaspiro[5.5]undecane-1,3,5,9-tetraones and 3-thioxo-2,4- diazaspiro[5.5]undecane-1,5,9-triones have been synthesized via double Michael addition of 1,5-diaryl-1,4-pentadien-3-one with active methylene compounds such as N,N-dimethyl barbituric acid, barbituric acid, thio-barbituric acid and N,N-diphenyl thiobarbituric acid in ethylene glycol at 100C in the absence of any catalyst to give high yields within a short reaction time. The structure has been confirmed by X-ray analysis. The single-crystal structure of the diazaspiro compound revealed that the CAr-H…pi, pi-pi stacking and intermolecular hydrogen bonding interactions act as major driving forces for crystal packing. This journal is the Partner Organisations 2014.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Hydrogenation of olefins using Hantzsch ester catalyzed by palladium on carbon

Hantzsch 1,4-dihydropyridine (HEH), a well-known model compound of coenzyme NAD(P)H was found as an efficient reducing agent in hydrogenation of unactivated olefins catalyzed by Pd/C. alpha,beta-Unsaturated ketones also underwent hydrogenation, affording the corresponding saturated ketones selectively.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Iridium NHC based catalysts for transfer hydrogenation processes using glycerol as solvent and hydrogen donor

A series of iridium and ruthenium N-heterocyclic carbene based catalysts of general formula [IrI2(AcO)(bis-NHC)] or [Ru(eta6-arene) (NHC)CO3] have been tested in the reduction of several organic carbonyl compounds using glycerol as solvent and hydrogen donor, by the transfer hydrogenation methodology. The Ir(III) complexes with a chelating bis-NHC ligand and sulfonate groups were the most efficient, due to their solubility in the reaction media and to the strong electron-donor properties of the bis-carbene ligands. The same two catalysts were moderately active in the reduction of olefins and alkynes and, more remarkably, show excellent chemoselectivity in the reduction of the alkenic double bond of alpha,beta-unsaturated ketones, a valuable process for which glycerol had never been used before.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Tandem hydrogenation and condensation of fluorinated alpha,beta-unsaturated ketones with primary amines, catalyzed by nickel

A simple homogeneous catalytic system based on nickel phosphine complexes has been developed for the transfer hydrogenation and condensation of alpha,beta-unsaturated ketones to yield saturated ones and saturated imines using primary amines as hydrogen donors. Thus, a wide range of fluorinated 1,5-diaryl-1,4-pentadiene-3-ones were allowed to react with substituted benzylamines in the presence of [(dippe)Ni(mu-H)]2 (dippe = 1,2-bis-(diisopropylphosphino)-ethane) using ethanol as a solvent at 180 C to give the corresponding saturated carbonyl compounds; here hydrogenation of the CC bond was preferred over the CO bond. Under the same reaction conditions but using an excess of benzylamine, a tandem process is then favoured, starting also with the reduction of the CC bond followed by a nucleophilic addition of the primary amine to yield valuable saturated imines with good to excellent yields (62%-91%).

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Palladium Nanoparticles in Polyols: Synthesis, Catalytic Couplings, and Hydrogenations

Alcohols, in particular polyols, are well-known for the synthesis of metal nanoparticles, often acting as reducing agents, solvents, and stabilizers. Given not only their structural flexibility depending on the number of OH functions and their inherent H bonding interactions, but also the wide range of polyol molecular weights readily available, different physicochemical properties (boiling point, polarity, viscosity) could be exploited toward the synthesis of well-defined nanomaterials. In particular, the relevance of the supramolecular structure of polyols has a fundamental impact on the formation of metal nanoparticles, thereby favoring the dispersion of the nanoclusters. In the field of the metal-based nanocatalysis, palladium occupies a privileged position mainly due to its remarkable versatility in terms of reactivity representing a foremost tool in synthesis. In this review, we describe the controlled synthesis of Pd-based nanoparticles in polyol medium, focusing on the progress in terms of tailoring size, morphology, structure, and surface state. Moreover, we discuss the use of palladium nanoparticles, in a polyol solvent, applied in two of the most relevant Pd-catalyzed processes, i.e., couplings and hydrogenation reactions, including multistep processes.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate

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Spectral characterization and crystal structure of some 2,6-diarylthian-4-one hydrazone derivatives

A series of cis and trans 2,6-diarylthian-4-one hydrazone derivatives (11-16) have been synthesized and characterized by 1H, 13C and two dimensional NMR spectroscopy. For the 2r,6t-diphenylthian-4-one N-isonicotinoylhydrazone (14) X-ray diffraction have also been recorded. The coupling constants suggested that the cis-hydrazones (11-13), which have the phenyl groups in cis orientation, largely exist in chair conformations with equatorial orientation of the phenyl groups 11C. Analysis of the vicinal coupling constants of trans-hydrazones (14-16) suggests that boat forms 14B must make significant contributions to it and the relative population is 58%. Moreover, in solution chair conformations 14C and 14C?, may contribute to 14. The NOESY and X-ray diffraction of 14 gives definite evidence for the contribution of 14C.

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Reference£º
Synthesis and Crystal Structure of a Chiral?C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur¨Cnitrogen¨Coxygen ligand derived from aminothiourea and sodium?D-camphor-¦Â-sulfonate