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Palladium-Catalyzed Conjugate Addition Type Reaction of Aryl Iodides with alpha,beta-Unsaturated Ketones

Aryl iodides have been found to react with alpha,beta-unsaturated ketones in the presence of catalytic amounts of palladium, an excess of formic acid, and triethylamine, giving rise to conjugate addition type products.The electron-withdrawing power of the group attached to the olefinic double bond, the substituent beta to the carbonyl group, and the basic reaction medium appear to effect greatly the conjugate addition/vinylic substitution ratio.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Preparation of N,N-bis(trimethylsilyl)-1-alkenesulfenamides and their desilylative conversion to 1-alkenesulfenimines. New stable 1-alkenesulfenic acid derivatives

Eight stable N,N-bis(trimethylsilyl)-1-alkenesulfenamides (3) were synthesized by the reaction of 1-alkenesulfenate anions with TMSCI and LiHMDS. Compounds 3 were isolated either by distillation or by chromatography. 1-Alkenesulfenamides (3) can be desilylated in the presence of aldehydes and ketones that do not bear alpha- hydrogens, to afford 1-alkenesulfenimines (7) either as single isomers or as mixtures of geometric isomers about the C=N bond. Protodesilylation of compounds 3 leads to 1-alkenesulfenamides (8) that have only hydrogens on the nitrogen. The parent 1- alkenesulfenamides 8 are not particularly stable, but could be characterized.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Room-Temperature Direct beta-Arylation of Thiophenes and Benzo[b]thiophenes and Kinetic Evidence for a Heck-type Pathway

The first example of a regioselective beta-arylation of benzo[b]thiophenes and thiophenes at room temperature with aryl iodides as coupling partners is reported. This methodology stands out for its operational simplicity: no prefunctionalization of either starting material is required, the reaction is insensitive to air and moisture, and it proceeds at room temperature. The mild conditions afford wide functional group tolerance, often with complete regioselectivity and high yields, resulting in a highly efficient catalytic system. Initial mechanistic studies, including 13C and 2H KIEs, suggest that this process occurs via a concerted carbo-palladation across the thiophene double bond, followed by a base-assisted anti-elimination.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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On the origin of changes in topicity observed in Diels-Alder reactions catalyzed by Ti-TADDOLates

New C2 symmetric TADDOLs containing different groups at the 2-position of the dioxolane ring have been prepared. The Ti catalysts derived from these have been studied in the Diels-Alder reaction of cyclopentadiene and (E)-2-butenoyl-1,3-oxazolidin-2-one. Substituents at the C-2 position of the dioxolane ring can play an important role in determining the selectivity as well as the nature of the major isomer. This effect is more important for TADDOLs containing bulky aromatic groups such as 3,5-dimethylphenyl- or 1-naphthyl at the alpha-positions. Experimental evidence supports the hypothesis that pi-pi interactions between aromatic groups at the C-2 and the ones at the alpha-positions are critical in this respect.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Synthesis and anticonvulsant activity of some spiro compounds derived from barbituric and thiobarbituric acids: Part I

Divinyl ketones (1), prepared by the condensation of acetone with the appropriate aromatic aldehydes, on Michael addition with barbituric and thiobarbituric acids afford the desired spiro compounds (2a-j). The ketoximes (3a-j) obtained from 2a-j on Beckmann transformation by treatment with PCl5 furnish the spiro azepines (4a-j). Alkylation of some of the compounds 2 afford the anticipated N-substituted products (5a-i). Preliminary pharmacological screening of some of the new compounds reveal their anticonvulsant activity.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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NEW ASPECTS OF THE CHEMISTRY OF 2,3-DIHYDRO-1H-1,5-BENZODIAZEPINE

Under basic catalysis conditions the reaction of 4- and 4′-substituted chalcones with o-phenylenediamine leads to 2,3-dihydro-2,4-diaryl-1H-1,5-benzodiazepines; beta-amino adducts, the ability of which to undergo intramolecular condensation increases as the basicity of the catalyst is increased, are formed as intermediates.A different pathway for the process (the formation of an azomethine) is observed in the reaction with cinnamaldehyde.It is concluded that conformational factors play a primary role in the direction of the reaction.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Formal diels-alder reactions of chalcones and formylcyclopropanes catalyzed by chiral n-heterocyclic carbenes

Highly enantioselective (formal) hetero-Diels-Alder reactions between chalcones and formylcyclopropanes are disclosed. The challenging N-heterocyclic carbene (NHC)-bounded enolate intermediates from formylcyclopropanes were captured for new C-C bond forming reactions. The reaction products were obtained with high diastereo- and enantioselectivities and could be easily transformed to optically pure multisubstituted cyclohexane derivatives.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Chemoselective double Michael addition: Synthesis of 2, 6-diarylspiro[cyclohexane-1,3′-indoline]-2′,4-diones via addition of indolin-2- one to divinyl ketones

Seventeen examples of 2,6-diarylspiro[cyclohexane-1,3′-indoline]-2′,4-diones were efficiently prepared by the Cs2CO3-catalysed chemoselective double Michael additions of indolin-2-one to divinyl ketones. This method has the advantage of high chemoselectivity, mild reaction conditions, high yield and atom- and step-economy.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-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:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Chemoselective transfer hydrogenation of alpha,beta-unsaturated carbonyls using palladium immobilized ionic liquid catalyst

This work reports a simple and highly efficient protocol for chemoselective transfer hydrogenation of alpha,beta-unsaturated carbonyls using immobilized palladium metal-containing ionic liquid as a versatile heterogeneous catalyst with an excellent conversion and chemoselectivity (up to 100 %). The influence of various reaction parameters such as the effect of hydrogen donor, solvent, temperature, and time were studied. The catalyst was recycled for four consecutive cycles without significant loss in the catalytic activity. The developed protocol is more advantageous due to the use of HCOONH4 as a hydrogen source, mild reaction conditions, and simple workup procedure and applicable for a wide range of substrates.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate