Stereoselective Synthesis of 1,5-Diionic Organophosphorus Compounds

The reactive 1:1 intermediate produced in the reaction between triphenylphosphine and alkyl propiolates or ethynyl phenyl ketone was trapped by isopropylidene Meldrum's acid (5-isopropylidene-2,2-dimethyl-1,3-dioxane-4,6-dione) to produce alkyl 3-(isopropylidenemalonate-5-yl-5-ylid)-3-methyl-2-triphenylphosphoniomethylidene-butanoates or 3-(isopropylidenemalonate-5-yl-5-ylid)-3-methyl-2-triphenylphosphoniomethylidene-butanone in 75-86% yield. These 1,5-diionic phosphorus betaines exist as (Z) geometrical isomer in CDCl 3 solution.     

A Facile One-Pot Synthesis of Highly-Functionalized Stable Heterocyclic Phosphorus Ylides in Aqueous Media

Phthalimide or succinimide undergo a reaction with dialkyl acetylenedicarboxylates and triphenylphosphine to produce highly-functionalized stable heterocyclic phosphorus ylides in good yields in water-tetrahydrofuran (6:1). This methodology is of interest because of the use of water as solvent, thus minimizing the cost, operational hazards, and environmental pollution.     

Microwave-Assisted Chemoselective Regeneration of Carbonyl Compounds from Oximes by Silica Chromate/WET SiO2 Under Solvent-Free Conditions

The regeneration of carbonyl compounds from oximes were performed by using silica chromate and wet SiO ₂ (w/w 50%) under microwave irradiation and solvent-free conditions with excellent yields.     

Melamine Trisulfonic Acid (MTSA): A New Efficient Catalyst for the Chemoselective Methoxymethylation of Alcohols

Melamine trisulfonic acid, which is easily prepared by the reaction of melamine with neat chlorosulfonic acid, is able to efficiently catalyze the chemoselective methoxymethylation of alcohols with dimethoxymethane (DMM). All reactions were performed under mild and completely heterogeneous reaction conditions in good to high yields.     

Convenient Synthesis of 2-Aminothiophene Derivatives by Acceleration of Gewald Reaction Under Ultrasonic Aqueous Conditions

Under ultrasound irradiation and in the presence of H₂O/Et₂NH, ethyl cyanoacetate or malononitrile can combine with α-methylene carbonyl compounds and elemental sulfur to efficiently yield 2-aminothiophene derivatives within a few minutes. Products are easily obtained by simple filtration because of their spontaneous precipitation in the reaction mixtures.     

Simple and Highly Efficient Procedure for Conversion of Aldoximes to Nitriles Using N-(p-Toluenesulfonyl) Imidazole

A facile and efficient method for dehydration of aldoximes into nitriles using N-(p-toluenesulfonyl) imidazole (TsIm) is described. In this method, aldoximes were refluxed with TsIm in the presence of 1,8-diazabicyclo-[5.4.0]undec-7-ene (DBU) in dimethylformamide (DMF) to afford the corresponding nitriles in good yields. This methodology is highly efficient for various structurally diverse aldoximes including aromatic, heteroaromatic, and aliphatic oximes. A plausible mechanism for the conversion of aldoxime into nitriles using TsIm/DBU is explained.     

KG-60-Piperazine as a New Heterogeneous Catalyst for Gewald Three-Component Reaction

Piperazine supported on amorphous silica (KG-60-piperazine) as a basic catalyst acts in the Gewald three-component reaction of some aldehydes and ketones with malononitrile as well as ethyl cyanoacetate. The catalyst shows general utility with a variety of starting carbonyl compounds. Moreover, the catalyst can be reused for four additional cycles without significant loss of the activity.

Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.     

Hydrogen Bonding in Aprotic Solvents,a New Strategy for Gelation of Bioinspired Catecholic Copolymers with N‐Isopropylamide

Copolymers of N‐isopropylacrylamide (NIPAM) and dopamine methacrylate can establish a reversible, self‐healing 3D network in aprotic solvents based on hydrogen bonding. The reactivity and hydrogen bonding formation of catechol groups in copolymer chains are studied by UV–vis and ¹H NMR spectroscopy, while reversibility from sol to gel and inverse as well as self‐healing properties are tested rheologically. The produced reversible organogel can self‐encapsulate physically interacting or chemically bonded solutes such as drugs due to thermosensitivity of the used copolymer. This system offers dual‐targeted and controlled drug delivery and release—by slowing down release kinetics by supramolecular bonding of the drug and by reducing diffusion rates due to modulus increase.

     

Peripherally and Axially Carboxylic Acid Substituted Subphthalocyanines for Dye‐Sensitized Solar Cells

A series of subphthalocyanines (SubPcs) bearing a carboxylic acid group either at the peripheral or axial position have been designed and synthesized to investigate the influence of the COOH group positions on the dye‐sensitized solar cell (DSSC) performance. The DSSC devices based on SubPcs with axially substituted carboxylic acid groups showed low photovoltaic performance, whereas peripherally substituted one exhibited higher power conversion efficiency owing to improved injection from LUMO of SubPcs to the TiO₂ conduction band.     

Electrochemically Generated Nanoparticles of Halogen‐Bridged Mixed‐Valence Binuclear Metal Complex Chains

Spherical nanoparticles composed of MMX chains can be made by a polymerization strategy driven by electrochemical processes. In particular, the [Pt₂(MeCS₂)₄I₂] (MMI₂) dimetal subunit is employed as a monomer for the formation of [Pt₂(MeCS₂)₄I]_n spherical nanostructures on surfaces. We have paid particular attention to elucidating the general mechanism of the deposition process on the basis of in situ electrochemical measurements. The reduction of MMI₂ to give the electrodeposition of nanostructures agrees well with formation of the reduced [MMI₂]^? species followed by a disproportionation mechanism mediated by iodide anions. The chemical composition of the particles was determined by energy‐dispersive X‐ray spectroscopy (EDX) and X‐ray photoelectron spectroscopy (XPS) to reveal the MMI₂ polymer.