Acid?Base Properties of Adenosine 5′‐Monophosphate,Guanosine 5′‐Monophosphate,and Inosine 5′‐Monophosphate in Aqueous Solutions of Methanol

The protonation constants of adenosine 5′‐monophosphate, guanosine 5′‐monophosphate, and inosine 5′‐monophosphate were determined in binary mixtures of H₂O containing 0, 10, 15, 20, 25, 30, 35, 40, 45, and 50% MeOH, using a combination of potentiometric and spectrophotometric methods at a constant temperature (25°) and constant ionic strength (0.1 mol?dm^?3 NaClO₄). The protonation constants were analyzed using the normalized polarity parameter (E ), and Kamlet, Abboud, and Taft (KAT) parameters. A linear correlation of log K vs. the normalized polarity parameter was obtained. Dual‐parameter correlation of log K vs. π* (dipolarity/polarizability) and α (H‐bond‐donor acidity), as well as π* and β (H‐bond‐acceptor basicity) also gives good results in various aqueous organic solvent mixtures. Finally, the results are discussed in terms of the effect of solvent on the protonation equilibria.     

A Facile Synthesis of a Wide Variety of Cationic Ruthenium Hydrido‐Arene Complexes of binap (=1,1′‐Binaphthalene‐2,2′‐diylbis(diphenylphosphane)) and MeO?biphep (=6,6′‐Dimethoxybiphenyl‐2,2′‐diylbis(diphenylphosphane))

A straightforward high‐yield synthetic route to the cationic hydrido‐arene complexes [RuH(η⁶‐arene)(binap or MeO biphep)](CF₃SO₃), with a variety of arenes containing both donor and acceptor substituents, is described. ¹³C‐NMR Data for these complexes are reported. Several of these Ru‐complexes have been used as transfer‐hydrogenation catalysts in the reduction of acetophenone.     

Synthesis of 1H,7H,12bH‐Pyrano[3′,4′: 5,6]pyrano[3,4‐c][1]benzopyran‐1‐one via Domino Knoevenagel/Hetero‐Diels?Alder Reaction with Theoretical Investigations

The CuI‐catalyzed intramolecular oxa‐Diels? Alder reaction of 2‐(prop‐2‐yn‐1‐yloxy)benzaldehydes as unactivated terminal alkynes with 4‐hydroxy‐6‐methyl‐2H‐pyran‐2‐one is described. The reaction proceeds with remarkable chemoselectivity to yield pyranones 3 (Scheme 1). A theoretical investigation of the reaction in terms of HOMO? LUMO interactions in the gas phase is also reported. The reaction could be regarded as an inverse‐electron‐demand Diels? Alder cycloaddition. The theoretical results are in high agreement with the experimental evidences.     

Warum pentose-und nicht hexose-nucleinsäuren? Teil III. Oligo(2′,3′-dideoxy-β-D-glucopyranosyl) nucleotide (‘homo-DNS’): Paarungesigenschaften

Why Pentose-And Not Hexose-Nucleic Acids? Part III. Oligo(2′,3′-dideoxy-β-D -glucopyranosyl)nucleotides. (‘Homo-DNA’): Base-Pairing Properties

1 Summary in collaboration with Prof. Dr. C. E. Wintner, Haverford College, Haverford, PA 19041-1392.

The paper presents results of a comprehensive investigation on the pairing properties of homo-DNA oligonucleotides, the preparation of which has been described in Part II of this series [2]. The investigation was carried out by using established methods described in the literature for the characterization of oligonucleotides in the natural series, such as determination of melting temperatures of oligonucleotide duplexes by temperature-dependent of melting temperatures, determination of pairing stoichiometry by ratio-dependent UV spectroscopy of binary mixtures of pairing partners, temperature-dependent CD spectroscopy, gel electrophoresis under non-denaturing conditions, and – in selected cases – ¹H – and³¹P-NMR spectroscopy. The systematic comparison of the paring properties of homo-DNA oligonucleotides with corresponding DNA nucleotides (up to dodecamers) indicates that homo-DNA is a highly efficient, autonomous, artificial pairing system with a pairing behavior that is in part similar to, but also, in part, strikingly different from, the pairing behavior of DNA. The pairing properties established so far are listed below in a manner that reflects the sequence of subtitles in Chapt.2 of the text; they were determined under the conditions: H²O, 0.15M NaCl, 0.01M Tris-HCl buffer, pH 7, oligonucleotide concentrations in the μM range, 1:1 ratio of single strands in the case of non-selfcompementary sequences.     

Multicenter Homogeneous Dendritic Catalysts: The Higher the Generation,the Better the Reactivity and Selectivity? – A Comparative Study of the Catalytic Efficiency of Dendrimeric [1,1′‐Binaphthalene]‐2,2′‐diol‐Derived Catalysts

The G0 and G1 generations of optically active, multicenter 1,1′‐binaphthalene‐based dendritic ligands 4 and 5 constructed on a rigid oligo(arylene) framework were prepared by divergent synthesis. Their corresponding aluminum complexes 1 and 2 , respectively, were shown to possess slightly better reactivity and enantioselectivity than those of a monomeric 1,1′‐binaphthalene catalyst 3 in the Diels–Alder reaction between cyclopentadiene and 3‐[(E)‐but‐2‐enoyl]‐oxazolidin‐2‐one.     

Practical Metal‐Free C(sp3)?H Functionalization: Construction of Structurally Diverse α‐Substituted N‐Benzyl and N‐Allyl Carbamates

Described is a practical and universal C H functionalization of readily removable N‐benzyl and N‐allyl carbamates, with a wide range of nucleophiles at ambient temperature promoted by Ph₃CClO₄. The metal‐free reaction has an excellent functional‐group tolerance, and displays a broad scope with respect to both N‐carbamates and nucleophile partners (a variety of organoboranes and C H compounds). The synthetic utility in target‐ as well as diversity‐oriented syntheses is demonstrated.     

Removal and Recovery of UO2(??) from Water Samples Using 2,2′‐Diamino‐4,4′‐bithiazole as a New Reagent for Solid Phase Extraction

A novel sensitive and simple method for rapid and selective extraction, preconcentration and determination of uranyl as its 2,2′‐diamino‐4,4′‐bithiazole (DABTZ) complex by using octadecylsilica columns and spectrophotometry is presented. Extraction efficiency and the influence of flow rates of sample solution and eluent, pH, amount of DABTZ, type and least amount of eluent for elution of uranyl complex from columns, break‐through volume and limit of detection were evaluated. Also the effects of various cationic and anionic interferences on percent recovery of uranyl were studied. Average extraction efficiency of ca. 90% was obtained by elution of the column with minimal amount of solvent in the presence of interferences. The average preconcentration factor, 136 and a detection limit 0.32 ng·mL^?1 were obtained. The method was applied to the recovery and determination of uranyl in different water samples.     

Bis(4‐picoline‐κN)gold(I) dibromidoaurate(I) and bis(4‐picoline‐κN)gold(I) dichloridoaurate(I): space‐group ambiguity?

Bis(4‐picoline‐κN)gold(I) dibromidoaurate(I), [Au(C₆H₇N)₂][AuBr₂], (I), crystallizes in the monoclinic space group P2₁/n, with two half cations and one general anion in the asymmetric unit. The cations, located on centres of inversion, assemble to form chains parallel to the a axis, but there are no significant contacts between the cations. Cohesion is provided by flanking anions, which are connected to the cations by short Au...Au contacts and C—H...Br hydrogen bonds, and to each other by Br...Br contacts. The corresponding chloride derivative, [Au(C₆H₇N)₂][AuCl₂], (II), is isotypic. A previous structure determination of (II), reported in the space group P with very similar axis lengths to those of (I) [Lin et al. (2008). Inorg. Chem. 47 , 2543–2551], might be identical to the structure presented here, except that its γ angle of 88.79 (7)° seems to rule out a monoclinic cell. No phase transformation of (II) could be detected on the basis of data sets recorded at 100, 200 and 295 K.     

Rhodium(III)‐Catalyzed ortho Alkenylation of N‐Phenoxyacetamides with N‐Tosylhydrazones or Diazoesters through C?H Activation

A coupling reaction of N‐phenoxyacetamides with N‐tosylhydrazones or diazoesters through Rh^III‐catalyzed C H activation is reported. In this reaction, ortho‐alkenyl phenols were obtained in good yields and with excellent regio‐ and stereoselectivity. Rh–carbene migratory insertion is proposed as the key step in the reaction mechanism.     

Rydberg or Valence? The Long‐Standing Question in the UV Absorption Spectrum of 1,1′‐Bicyclohexylidene

The electronic excited states of the olefin 1,1′‐bicylohexylidene (BCH) are investigated using multiconfigurational complete active space self‐consistent‐field second order perturbation theory in its multi‐state version (MS‐CASPT2). Our calculations undoubtedly show that the bulk of the intensity of the two unusually intense bands of the UV absorption of BCH measured with maxima at 5.95 eV and 6.82 eV in the vapor phase are due to a single ππ* valence excitation. Sharp peaks reported in the vicinity of the low‐energy feature in the gas phase correspond to the beginning of the π3s_R Rydberg series. By locating the origin of the ππ* band at 5.63 eV, the intensity and broadening of the observed bands and their presence in solid phase is explained as the vibrational structure of the valence ππ* transition, which underlies the Rydberg manifold as a quasi‐continuum.     

Luminescent Amphiphilic 2,6‐Bis(1,2,3‐triazol‐4‐yl)pyridine?Platinum(II) Complexes: Synthesis,Characterization, Electrochemical,Photophysical, and Langmuir–Blodgett Film‐Formation Studies

A new series of platinum(II) complexes with tridentate ligands 2,6‐bis(1‐alkyl‐1,2,3‐triazol‐4‐yl)pyridine and 2,6‐bis(1‐aryl‐1,2,3‐triazol‐4‐yl)pyridine (N7R), [Pt(N7R)Cl]X ( 1 – 7 ) and [Pt(N7R)(C?CR′)]X ( 8 – 17 ; R=n‐C₄H₉, n‐C₈H₁₇, n‐C₁₂H₂₅, n‐C₁₄H₂₉, n‐C₁₈H₃₇, C₆H₅, and CH₂‐C₆H₅; R′=C₆H₅, C₆H₄‐CH₃‐p_, C₆H₄‐CF₃‐p, C₆H₄‐N(CH₃)₂‐p, and cholesteryl 2‐propyn‐1‐yl carbonate; X=OTf^?, PF₆^?, and Cl^?), has been synthesized and characterized. Their electrochemical and photophysical properties have also been studied. Two amphiphilic platinum(II)? 2,6‐bis(1‐dodecyl‐1,2,3‐triazol‐4‐yl)pyridine complexes ( 3‐Cl and 8 ) were found to form stable and reproducible Langmuir–Blodgett (LB) films at the air/water interface. These LB films were characterized by the study of their surface‐pressure–molecular‐area (π–A) isotherms, XRD, and IR and polarized‐IR spectroscopy.     

A Straightforward Synthesis of 2‐[1‐Alkyl‐5,6‐bis(alkoxycarbonyl)‐1,2,3,4‐tetrahydro‐2‐oxopyridin‐3‐yl]acetic Acid Derivatives via Domino Michael Addition?Cyclization Reaction

A new and efficient synthesis of 2‐[1‐alkyl‐5,6‐bis(alkoxycarbonyl)‐1,2,3,4‐tetrahydro‐2‐oxopyridin‐3‐yl]acetic acid derivatives by a one‐pot three‐component reaction between primary amine, dialkyl acetylenedicarboxylate, and itaconic anhydride (=3,4‐dihydro‐3‐methylidenefuran‐2,5‐dione) is reported. The reaction was performed without catalyst and under solvent‐free conditions with excellent yields. Notably, the ready availability of the starting materials, and the high level of practicability of the reaction and workup make this approach an attractive complementary method to access to unknown 2‐[1‐alkyl‐5,6‐bis(alkoxycarbonyl)‐1,2,3,4‐tetrahydro‐2‐oxopyridin‐3‐yl]acetic acid derivatives. The structures were corroborated spectroscopically (IR, ¹H‐ and ¹³C‐NMR, and EI‐MS) and by elemental analyses. A plausible mechanism for this type of domino Michael addition? cyclization reaction is proposed (Scheme 2).     

Redox‐Triggered C?C Coupling of Diols and Alkynes: Synthesis of β,γ‐Unsaturated α‐Hydroxyketones and Furans by Ruthenium‐Catalyzed Hydrohydroxyalkylation

Direct ruthenium‐catalyzed C C coupling of alkynes and vicinal diols to form β,γ‐unsaturated ketones occurs with complete levels of regioselectivity and good to complete control over the alkene geometry. Exposure of the reaction products to substoichiometric quantities of p‐toluenesulfonic acid induces cyclodehydration to form tetrasubstituted furans. These alkyne‐diol hydrohydroxyalkylations contribute to a growing body of merged redox‐construction events that bypass the use of premetalated reagents and, hence, stoichiometric quantities of metallic by‐products.