Selective methylative homologation: an alternate route to alkane upgrading

InI3 catalyzes the reaction of branched alkanes with methanol to produce heavier and more highly branched alkanes, which are more valuable fuels. The reaction of 2,3-dimethylbutane with methanol in the presence of InI3 at 180-200 degrees C affords the maximally branched C7 alkane, 2,2,3-trimethylbutane (triptane). With the addition of catalytic amounts of adamantane the selectivity of this transformation can be increased up to 60%. The lighter branched alkanes isobutane and isopentane also react with methanol to generate triptane, while 2-methylpentane is converted into 2,3-dimethylpentane and other more highly branched species. Observations implicate a chain mechanism in which InI3 activates branched alkanes to produce tertiary carbocations which are in equilibrium with olefins. The latter react with a methylating species generated from methanol and InI3 to give the next-higher carbocation, which accepts a hydride from the starting alkane to form the homologated alkane and regenerate the original carbocation. Adamantane functions as a hydride transfer agent and thus helps to minimize competing side reactions, such as isomerization and cracking, that are detrimental to selectivity.     

Insight into the reduction of pyruvic acid to lactic acid over Cu{110}: the crucial role of intramolecular tunneling in direct hydrogenation

This work presents results from density functional theory calculations which are used to elucidate the reduction of pyruvic acid to lactic acid by direct hydrogenation over Cu{110} in vacuo. We propose a plausible pathway from reactants to products that crucially relies upon an intramolecular tunneling step to circumvent energetically unfavorable hydrogen exchange with the surface. The conclusions are further augmented by analyzing the electron density and frontier orbitals of key reaction intermediates. This reveals the origin of the predicted activity to be intimately linked to the electronic structure, which in turn is dependent upon the asorption geometry of pyruvic acid. Through the use of equilibrium thermodynamics, we are able to show the influence of temperature and pressure on the reaction profile. Importantly showing, that as the temperature is raised at low pressure (1 x 10(-10) mbar), so the rate-determining step switches from being the carbonyl reduction to the reprotonation of the carboxylate group (leading to the desorption of lactic acid). At ambient pressure of 1 bar, the influence of temperature on the relative barrier heights is much less significant. This is an important step in attempting to bridge the so-called "pressure gap" and opens up the possibility of understanding the reactivity of small biologically relevant molecules at metal surfaces.     

Recent developments in ambient ionization techniques for analytical mass spectrometry

Ambient ionization techniques enable the interrogation of a variety of samples in their native state by mass spectrometry, and are rapidly advancing all fields where screening for the presence of various analytes in a broadband and/or high-throughput fashion is desirable. This Highlight article provides an introduction to the field, and showcases the different ionization approaches reported since 2004, with an emphasis on the most recent developments.     

endo-Selective (3+2) cycloaddition polymerizations of nitrone monomers with olefins utilising high pressure conditions

A high pressure mediated (3+2) cycloaddition polymerization strategy has been employed to afford linear poly(isoxazolidine) architectures. Under these high pressure conditions this cycloaddition process was found to afford primarily endo-heterocycles which when translated to the polymerization should ultimately affect the tacticity and resultant properties of the polymer. The stereoselectivity occurred as a result of a lower volume of activation for the endo-transition state and the application of a ‘type-I’ regime (HOMO_Dipole-LUMO_{Dipolarophile}) cycloaddition process that features secondary orbital interactions within the extended molecular orbitals. A variety of linker segments were employed in an attempt to affect the physical properties of the polymeric cycloadducts such as T_g and solubility in order to tailor these materials for use in coating applications.     

Metal-assisted in situ formation of a tridentate acetylacetone ligand for complexation of fac-Re(CO)3+ for radiopharmaceutical applications

Reaction of [NEt4]2[ReBr3(CO)3] with 2,4-pentanedione (acac) yields a complex of the type fac-Re(acac)(OH2)(CO)3 (1) under aqueous conditions. 1 was further reacted with a monodentate ligand (pyridine) to yield a fac-Re(acac)(pyridine)(CO)3 complex (2). Complex 1 was found to react with primary amines to generate a Schiff base (imine) in aqueous solutions. When a mixed-nitrogen donor bidentate ligand, 2-(2-aminoethyl)pyridine, that has different coordination affinities for fac-Re(acac)(OH2)(CO)3 was utilized, a unique tridentate ligand was formed in situ utilizing a metal-assisted Schiff base formation to yield a complex fac-Re(CO)3(3[(2-phenylethyl)imino]-2-pentanone) (3). Tridentate ligand formation was found to occur only with the Re-coordinated acac ligand. Reactions of acac with fac-Re(CO)3Br(2-(2-aminoethyl)pyridine) (4) or a mixture of [NEt4]2[ReBr3(CO)3], acac, and 2-(2-aminoethyl)pyridine did not yield the formation of complex 3 in water.     

Synthesis and thermal chemistry of copper (I) guanidinates

Copper (I) guanidinate dimers were generated by a salt metathesis route and structurally characterized. The guanidinates differed from the known amidinate dimers because of a large torsion of the dimer ring. This had a direct effect on their thermal chemistry. The thermal reactivity was investigated by several methods, including a novel temperature-resolved, gas-phase method that was monitored by mass spectrometry. The copper guanidinates underwent carbodiimide deinsertion to produce copper metal at temperatures between 225 -and 250 degrees C in the gas phase and at 125 degrees C in solution. The amidinate investigated also showed copper deposition at 190 degrees C in the gas phase, and 135 degrees C in solution, but without carbodiimide deinsertion. The guanidinate compounds deposited crystalline copper at 225 degrees C in a simple chemical vapor deposition experiment.     

New synthetic routes to a disulfidodinickel(II) complex: characterization and reactivity of a Ni2(mu-eta2:eta2-S2) core

Activation of elemental sulfur by the monovalent nickel complex [PhTt (tBu)]Ni(CO) [PhTt(tBu)=phenyl{tris[(tert-butylmethyl)thio]methyl}borate] generates the disulfidodinickel(II) complex 2. This species is alternatively accessible via thermal decomposition of [PhTt (tBu)]Ni(SCPh3). Spectroscopic, magnetic, and X-ray diffraction studies establish that 2 contains a mu-eta(2):eta(2)-S2 ligand that fosters antiferromagnetic exchange coupling between the Ni (II) ions. This observation is in contrast to the lighter congener, oxygen, which strongly favors the bis(mu-oxo)dinickel(III) structure. 2 oxidizes PPh 3 to SPPh3 and reacts with O2, generating several products, one of which has been identified as [(PhTt (tBu))Ni]2(mu-S) (3).     

Resolution and quantification of arginine,monomethylarginine, asymmetric dimethylarginine,and symmetric dimethylarginine in plasma using HPLC with internal calibration

N^G,N^G‐dimethyl‐l ‐arginine (asymmetric dimethylarginine, ADMA),N^G‐monomethyl‐l ‐arginine (l ‐NMMA) and N^G,N^G’‐dimethyl‐l ‐arginine (symmetric dimethylarginine, SDMA) are released during hydrolysis of proteins containing methylated arginine residues. ADMA and l ‐NMMA inhibit nitric oxide synthase by competing with l ‐arginine substrate. All three methylarginine derivatives also inhibit arginine transport. To enable investigation of methylarginines in diseases involving impaired nitric oxide synthesis, we developed a high‐performance liquid chromatography (HPLC) assay to simultaneously quantify arginine, ADMA, l ‐NMMA and SDMA. Our assay requires 12 μL of plasma and is ideal for applications where sample availability is limited. We extracted arginine and methylarginines with mixed‐mode cation‐exchange columns, using synthetic monoethyl‐l ‐arginine as an internal standard. Metabolites were derivatized with ortho‐phthaldialdeyhde and 3‐mercaptopropionic acid, separated by reverse‐phase HPLC and quantified with fluorescence detection. Standard curve linearity was ≥0.9995 for all metabolites. Inter‐day coefficient of variation (CV) values were ≤5% for arginine, ADMA and SDMA in human plasma and for arginine and ADMA in mouse plasma. The CV value for l ‐NMMA was higher in human (10.4%) and mouse (15.8%) plasma because concentrations were substantially lower than ADMA and SDMA. This assay provides unique advantages of small sample volume requirements, excellent separation of target metabolites from contaminants and validation for both human and mouse plasma samples. © 2015 The Authors Biomedical Chromatography published by John Wiley & Sons, Ltd.