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Modular Pincer-type Pyridylidene Amide Ruthenium(II) Complexes for Efficient Transfer Hydrogenation Catalysis

A set of bench-stable ruthenium complexes with new N,N,N-tridentate coordinating pincer-type pyridyl-bis(pyridylideneamide) ligands was synthesized in excellent yields, with the pyridylidene amide in meta or in para position (m-PYA and p-PYA, respectively). While complex [Ru(p-PYA)(MeCN)3]2+ is catalytically silent in transfer hydrogenation, its meta isomer [Ru(m-PYA)(MeCN)3]2+ shows considerable activity with turnover frequencies at 50% conversion TOF50 = 100 h-1. Spectroscopic, electrochemical, and crystallographic analyses suggest considerably stronger donor properties of the zwitterionic m-PYA ligand compared to the partially pi-acidic p-PYA analogue, imparted by valence isomerization. Further catalyst optimization was achieved by exchanging the ancillary MeCN ligands with imines (4-picoline), amines (ethylenediamine), and phosphines (PPh3, dppm, dppe). The most active catalyst was comprised of the m-PYA pincer ligand and PPh3, complex [Ru(m-PYA)(PPh3)(MeCN)2]2+, which reached a TOF50 of 430 h-1 under aerobic conditions and up to 4000 h-1 in the absence of oxygen. The presence of oxygen reversibly deactivates the catalytically active species, which compromises activity, but not longevity of the catalyst. Ligand exchange kinetic studies by NMR spectroscopy indicate that the strong trans effect of the phosphine is critical for high catalyst activity. Diaryl, aryl-alkyl, and dialkyl ketones were hydrogenated with high conversion, and alpha,beta-unsaturated ketones produced selectively the saturated ketone as the only product due to exclusive C=C bond hydrogenation, a distinctly different selectivity from most other transfer hydrogenation catalysts.

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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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Reversible cleavage of the C-H bond of aldimine with platinum complexes

The reversible cleavage of the C-H bond of aldimine with platinum complexes was studied. For the C-H oxidative addition to occur a heteroatom capable of coordinating to the metal center was necessary in the aldimine molecule. Systematic examinations on the thermodynamics and kinetics of both C-H bond oxidative addition and reductive elimination and catalytic application were presented.

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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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Photochemical transformations in some cyclopropyl ketones

Irradiation of trans-1-benzoyl-2-trans-styrylcyclopropane (IIa) and trans-1-p-toluoyl-2-trans-styrylcyclopropane (IIb), leads to formation of cis disubstituted cyclopropanes (IIIa) and (IIIb) respectively.However, photolysis of trans-1-trans-cinnamoyl-2-phenylcyclopropane (IV) results in isomerzation of the alpha,beta-double bond to produce V.Photolysis of trans-1-trans-p-methoxycinnamoyl-2-p-methoxyphenylcyclopropane (VI), by contrast, produces only a cyclobutane dimer formulated as (VII).Irradiation of 7-phenyl-3-benzylidenespiro<2.5>octan-2-one (IXb), under identical conditions, leads to isomerisation around the C=C bond.The structural assignments are based, interalia, on 13C NMR and 1H NMR spectral data.

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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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1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD) an efficient homogeneous catalyst for aldol condensation reactions. Study of the catalyst recovery and reusability using CO2

In this work it was shown that TBD (1,5,7-triazabicyclo[4.4.0]dec-5-ene), a cheap and commercially available guanidine base, efficiently catalyzes aldol condensation reactions yielding interesting products for pharmacological and fragrance industries. This methodology works under solvent-less conditions and affords with very good conversions the corresponding products. Moreover, a simple and effective separation protocol using the CO2 fixation was employed. The catalyst could be recovered and re-used for three consecutive runs without significant loss of activity.

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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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Asymmetric organocatalytic double-conjugate addition of malononitrile to dienones: Efficient synthesis of optically active cyclohexanones

9-Amino-9-deoxyepiquinine efficiently catalyzed the double-conjugate addition of malononitrile to dienones. A number of 1,1,2,6-tetrasubstituted cyclohexanones were prepared in good yields, diastereoselectivities, and excellent enantioselectivities.

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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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Enantioselective aza-Michael reaction of hydrazide to chalcones through the nonactivated amine moiety conjugated addition

The catalytic asymmetric aza-Michael reaction of benzoyl hydrazine toward chalcones through the nonactivated amine moiety conjugated addition was facilitated by the developed N,N?-dioxide-Sc(OTf)3 complex under mild conditions, affording the pharmacologically and synthetically useful products in moderate to high yields with up to 97% ee. The Royal Society of Chemistry.

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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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Microwave-assisted stereoselective 1,3-dipolar cycloaddition of C,N-diarylnitrone (i.e., N-(arylmethylidene)benzenamine N-oxide) and bis(arylmethylidene)acetone (=1,5-diarylpenta-1,4-dien-3-one): NMR and crystal analysis of diastereoisomeric bis(isoxazolidines)

Microwave-assisted stereoselective 1,3-dipolar cycloaddition of C,N-diarylnitrones (i.e., N-(arylmethylidene)benzenamine N-oxides) 2 to substituted bis(arylmethylidene)acetones (=1,5-diarylpenta-1,4-dien-3-ones) 1 leading to diastereoisomer pairs of bis-isoxazolidines 3 and 4 in good to excellent yield is described (Scheme2 and Table2). The configuration outcome of the reaction is discussed based on the NMR and X-ray data of the products. 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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Synthesis of optically enriched spirocyclic benzofuran-2-ones by bifunctional thiourea-base catalyzed double-michael addition of benzofuran-2-ones to dienones

A highly enantioselective catalytic double-Michael addition reaction of substituted benzofuran-2-ones with divinyl ketones promoted by readily accessible tertiary amine-thiourea Cinchona alkaloids has been developed. A number of optically enriched spirocyclic benzofuran-2-ones were prepared in very good yields (up to 99 %), diastereoselectivities (up to 19:1 d.r.), and very good enantioselectivities (up to 92 % ee). Density functional theory (DFT) calculations were performed to investigate the origin of stereoselectivity. A double take: A highly enantioselective catalytic double-Michael addition reaction of substituted benzofuran-2-ones with divinyl ketones promoted by readily accessible tertiary amine-thiourea Cinchona alkaloids has been developed. A number of optically enriched spirocyclic benzofuran-2-ones were prepared in very good yields (up to 99 %), diastereoselectivities (up to 19:1 d.r.), and very good enantioselectivities (up to 92 % 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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Penta- and decafluorinated dibenzalacetones: Synthesis, crystal structure, and cocrystallization experiments

The nonfluorinated parent dibenzalacetone 1 as well as the corresponding penta- (2) and decafluorinated (3) derivative compounds were prepared, crystallized, and subjected to co-crystallization experiments. Only 3 yielded a 1:1 co-crystal with 1, while 2 did not form co-crystals with either 1 or 3. Powder X-ray diffraction patterns were determined to verify the co-crystallization experiments. The influence of the fluorine on the molecular geometry and crystal packing were studied and comparatively discussed. Conclusions with reference to the priority of Ar…ArF contact modes in the crystalline packing being in competition with other fluorine and non-fluorine involved supramolecular interactions were drawn.

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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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Fe-catalyzed dithiane radical induced C?S bond activation?addition to alpha, beta-unsaturated ketones

An efficient and clean strategy to construct organosulfur compounds has been developed via a Fe-catalyzed dithiane C?S bond activation/addition process with alpha, beta-unsaturated ketones. This C?S activation protocol exhibits excellent reactivities, and up to 92% yield of the corresponding thioether-thioester derivatives could be obtained under the mild conditions, allowing the ready preparation of a number of synthetically valuable S-linked conjugates. (Figure presented.).

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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