A novel organocatalytic multi-component reaction: an efficient synthesis of polysubstituted pyrano-fused spirooxindoles

A practical, simple, and efficient method for the synthesis of pyrano-fused spirooxindoles via an organocatalytic three-component reaction of isatins, malononitrile, and dialkyl acetylenedicarboxylate in the presence of 3,4-dimethylaniline as an organocatalyst in ethanol is reported. The structures of these products are confirmed by IR, ¹H NMR and ¹³C NMR spectroscopy, mass spectrometry, and single-crystal X-ray diffraction studies.     

An Experimental Study of a Flux Modulated Solid State Metathesis Reaction

A solid state metathesis (SSM) reaction was investigated with respect to the formation of rare‐earth carbodiimides, the role of the co‐produced salt (LiCl), and the eutectic flux medium (LiCl/KCl). A SSM reaction is characterized by an exothermic reaction in which a salt (often LiCl) is coproduced. When the salt melts, it can serve as a useful medium for the crystallization of a desired product. An improved crystal growth can be observed by using an eutectic flux. However, the composition of an eutectic LiCl/KCl flux is altered when LiCl is produced during the reaction. The thermal effects concerning the endothermic melting of the flux and the exothermic ingnition of the SSM reaction may compensate each other, which is not necessarily a drawback for the reaction to proceed.     

An Efficient Four‐component Synthesis of Spiro[indoline‐pyrazolo[4′,3′:5,6]pyrido[2,3‐d]pyrimidine]triones

A four‐component reaction in the presence of Alum [KAl(SO₄)₂·12H₂O] as an inexpensive and reusable catalyst using the ionic liquid as an effective green reaction media is reported.     

Efficient synthesis of the C/D rings of atisine-type C20-diterpenoid alkaloids

A bicyclo[2.2.2]octane C/D ring system,with a lactonic ring at C-8 and C-9,of the atisine-type C₂₀-diterpenoid alkaloids,was successfully synthesized,using an oxidative dearomatization/intramolecular Diels-Alder reaction.     

An environmentally benign benzylic oxidation catalyzed by hypervalent iodine intermediate in water

An effective and environmentally benign benzylic oxidation for transition of alkylarenes into the corresponding carbonyl compounds was reported.Alkylarenes were mixed and stirred with potassium bromide,m-chloroperbenzoic acid and a catalytic amount of iodobenzene in water at 60 8C for several hours,a series of the corresponding carbonyl compounds was obtained in moderate to good yields.In the reaction,iodobenzene was first oxidized by m-chloroperbenzoic acid into the hypervalent iodine intermediate which then reacted with potassium bromide to form the key radical initiator for the benzylic oxidation.     

Amberlite IR-120 catalyzed,microwave-assisted rapid synthesis of 2-aryl-benzimidazoles

An expeditious synthesis of 2-aryl-benzimidazoles by the condensation of o-phenylenediamine with various araldehydes is described. This greener protocol is catalyzed by Amberlite IR-120, and proceeds efficiently in the absence of any organic solvent under microwave irradiation within 3–5 min.     

Hydrophobic Vitamin B12. X. Steric Effect in Electrochemical Carbon-Skeleton Rearrangement Catalyzed by Hydrophobic Vitamin B12 in Nonaqueous Media

Abstract

A steric effect in the carbon-skeleton rearrangement catalyzed by heptamethyl cobyrinate perchlorate, [Cob(II)7C₁ester]C10₄, was investigated under electrochemical conditions. The controlled-potential electrolyses of alkyl halides having two carboxylic ester groups of different bulkiness on the same carbon atom, such as 2,2-bis(ethoxycarbonyl)-l-bromopropane, l-bromo-2-tert-butoxycarbonyl-2-ethoxy-carbonylpropane, l-bromo-2-cyclohexyloxycarbonyl-2-ethoxycarbonylpropane, and l-bromo-2-ethoxy-carbonyl-2-phenoxycarbonylpropane, were carried out in N,N-dimethylformamide, as catalyzed by [Cob(II)7C₁ester]CIO₄, to give the corresponding ester-migrated products in the dark at—1.5 V vs SCE in the presence of acetic acid and at—2.0 V vs SCE without acetic acid. As regards a correlation between bulkiness of an ester group and a migration aptitude, a smaller ester group tends to migrate to the adjacent carbon atom more readily than a larger one. The origin of such a steric effect is discussed with attention to the rate-determining step.     

Synthesis and characterization of 1-phenyl-3-alkylbenzimidazol-2-ylidene salts and their catalytic activities in the Heck and Suzuki cross-coupling reactions

The synthesis and characterization of 1-phenyl-3-alkyl-substituted carbene precursors that were prepared from 1-phenyl substituted benzimidazole and various alkyl halides are reported. The new benzimidazolium salts (1a–e) were characterized by ¹H NMR, ¹³C NMR, FT-IR spectroscopic methods and elemental analyses. New in situ generated palladium-benzimidazolium complexes were tested for catalytic activity in the Mizoroki-Heck and Suzuki-Miyaura cross-coupling reactions.