p-Sulfonic acid calixarenes as efficient and reusable organocatalysts for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones/-thiones

AbstractA new and efficient methodology is proposed for obtaining 3,4-dihydropyrimidin-2(1H)-ones/-thiones through Biginelli reactions. It is based on the use of less than the stoichiometric amount of p-sulfonic acid calixarenes as organocatalysts. A number of aromatic aldehydes as well as urea or thiourea can be employed for successfully synthesizing the corresponding Biginelli adducts. The described methodology is devoid of metal-containing catalysts, which in turn is very attractive for safely producing 3,4-dihydropyrimidin-2-(1H)-ones/-thiones of pharmacological interest. In addition, the catalyst efficiency is not compromised after its successive use in reactions. This is the first report about the application of calixarenes as catalysts in the multicomponent Biginelli reaction

Dba-free" Palladium Intermediates Of The Heck-matsuda Reaction."

The dba-free Heck-Matsuda reaction was investigated via direct ESI-MS(/MS) monitoring. Palladium species involved in the reduction of Pd(II) during a Wacker type reaction and several dba-free arylpalladium transient complexes were detected and characterized. Based on these findings, a more comprehensible catalytic cycle for this pivotal reaction is suggested.113277-8

Synthesis of platinum and palladium complexes with bis-(hydroxy imines)

<p><em>The Schiff bases are an important class of compounds well used as ligands in coordination chemistry. The functionalized bis-imines, that represent a specific group of Schiff base, have been studied in our research group both for the evaluation of biological activity, against fungi and cancer, as for organocatalyst. Here the bis-imines <strong>1</strong> and <strong>4</strong> were synthesized in good yields by condensation of hydroxylated benzaldehydes with phenylenediamines. After that they were matched with Platinum and palladium salts providing three metallic complex (</em><strong>2</strong><em>, <strong>3</strong> and <strong>5</strong>) that were fully characterized by nuclear magnetic resonance and mass spectrometry with electrospray ionization. Now these complexes are being tested in cross-coupling reactions of Heck and Suzuki.</em></p

Gas Phase Chemistry Of The 2-tert-butyl-3-phenylphosphirenylium Cation: Novel Onium Ions By Nucleophilic Attack At Phosphorus And De Novo P-spiro Bicyclic Phosphonium Ions Via [4 + 2+] Cycloaddition With Dienes.

The 2-tert-butyl-3-phenylphosphirenylium ion 13 is formed in abundance in the gas phase from 1-chloro-1H-phosphirene 6 upon 70 eV electron ionization. Collision-induced dissociation (CID) and ion-molecule reactions followed by CID of the product ions were performed via pentaquadrupole mass spectrometry to probe the structure and reactivity of 13 towards representative nucleophiles and dienes. Under CID conditions, 13 produces a variety of fragment ions mainly via dissociation processes that are preceded by isomerizations. In ion-molecule reactions, 13 reacts readily with ethers, sulfides, pyridine and aniline to form hitherto unknown oxonium, sulfonium and azonium ions via nucleophilic attack at phosphorus. With butadiene, isoprene, 1-acetoxybutadiene, and with Danishefsky's diene (1-methoxy-3-silyloxybuta-1,3-diene), 13 undergoes [4 + 2+] cycloaddition at phosphorus to generate novel P-spiro bicyclic phosphonium ions. With butadiene and isoprene, a second [4 + 2] cycloaddition occurs which generates P-spiro tricyclic phosphonium ions. Whereas 13 also reacts readily with 1-acetoxybutadiene via[4 + 2+] cycloaddition, most of the nascent P-spiro cycloadducts are unstable and dissociate by the loss of either a neutral ketene or acetic acid molecule. B3LYP/6-31G(d,p) calculations were performed to gain insight into the structures of the product ions. The present study constitutes the first successful attempt to unravel the chemistry of 13, a unique 2 pi-Hückel phosphirenylium ion for which no direct solution chemical reactivity data are as yet available. The present findings also create a parallel with the solution reactivity of 1-halo-1H-phosphirenes and 1-triflato-1H-phosphirenes as precursors to phosphirenylium ions.1395-40

Probing The Mechanism Of The Heck Reaction With Arene Diazonium Salts By Electrospray Mass And Tandem Mass Spectrometry.

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ecoop2023_image.tar.gz

The artifact contains the extended versions of the tools angr and AVD with support for the symbolic reflection API proposed in the paper. Additionally, the artifact contains the source code of SumBoundVerify , our novel tool for the bounded-verification of symbolic summaries for the C programming language. The artifact contains all the scripts and datasets required to obtain the results presented in the paper "Toward Tool-Independent Summaries for Symbolic Execution", including: (1) a library of 67 symbolic summaries implemented using the proposed symbolic reflection API; (2) Two symbolic test suites designed to test two open source C libraries; and (3) the source code of the third-party summaries that were validated checked with SumBoundVerify.</h4

Dba-free palladium intermediates of the Heck-Matsuda reaction

The dba-free Heck-Matsuda reaction was investigated via direct ESI-MS(/MS) monitoring. Palladium species involved in the reduction of Pd(ii) during a Wacker type reaction and several dba-free arylpalladium transient complexes were detected and characterized. Based on these findings, a more comprehensible catalytic cycle for this pivotal reaction is suggested. © 2013 The Royal Society of Chemistry

Rhodium(III)-Catalyzed C–H/N–H Alkyne Annulation of Non-Symmetric 2-Aryl-(Benz)Imidazole Derivatives: Photophysical and Mechanistic Insights

Rhodium(III) catalysis enabled C–H/N–H alkyne annulation of nonsymmetric imidazole derivatives. This study encompasses the synthesis of imidazoles from a naturally occurring quinoidal compound and their use for the preparation of rigid π-extended imidazole derivatives with outstanding fluorescence. Our study also brings to light the photophysical aspects and the mechanism of the reaction studied via computational calculations. This method provided an efficient and versatile tool for the synthesis of fluorescent compounds with a wide range of chemical and biological applications

Identification Of Three Proteins That Associate In Vitro With The Leishmania (leishmania) Amazonensis G-rich Telomeric Strand.

The chromosomal ends of Leishmania (Leishmania) amazonensis contain conserved 5'-TTAGGG-3' telomeric repeats. Protein complexes that associate in vitro with these DNA sequences, Leishmania amazonensis G-strand telomeric protein (LaGT1-3), were identified and characterized by electrophoretic mobility shift assays and UV cross-linking using protein fractions purified from S100 and nuclear extracts. The three complexes did not form (a) with double-stranded DNA and the C-rich telomeric strand, (b) in competition assays using specific telomeric DNA oligonucleotides, or (c) after pretreatment with proteinase K. LaGT1 was the most specific and did not bind a Tetrahymena telomeric sequence. All three LaGTs associated with an RNA sequence cognate to the telomeric G-rich strand and a complex similar to LaGT1 is formed with a double-stranded DNA bearing a 3' G-overhang tail. The protein components of LaGT2 and LaGT3 were purified by affinity chromatography and identified, after renaturation, as approximately 35 and approximately 52 kDa bands, respectively. The <or= 15 kDa protein component of LaGT1 was gel-purified as a UV cross-linked complex of approximately 18-20 kDa. Peptides generated from trypsin digestion of the affinity and gel-purified protein bands were analysed by matrix-assisted laser desorption/ionization-time of flight and electrospray ionization tandem mass spectrometry. The fingerprint and amino acid sequence analysis showed that the protein components of LaGT2 and of LaGT3 were, respectively, similar to the kinetoplastid Rbp38p and to the putative subunit 1 of replication protein A of Leishmania spp., whereas the <or= 15 kDa protein component of LaGT1 was probably a novel Leishmania protein.2713050-6