The rate of dissociation of allyl iodide in shock waves

The rate of decomposition of allyl iodide has been measured from 742plusmn;K to 1068±K and from 169 to 1429 torr using a shock tube method in which the disappearance of allyl iodide and the appearance of iodine are followed simultaneously. The kinetics are first order in allyl iodide and probably are slightly dependent upon total pressure. Mathematical modeling shows that they are compatible with a mechanism consisting of three reactions: The experiments yield the rate constant k₁, the high-pressure limiting value of which is found to be in reasonable agreement with that predicted using the methods of Benson and O'Neal [1].     

Synthesis of a library of 2-alkyl-3-alkyloxy-2H-indazole-6-carboxamides

A library of 200 2-alkyl-3-alkyloxy-2H-indazole-6-carboxamides was synthesized using parallel solution-phase methods. The indazole cyclization reaction was optimized for library production with the best yields resulting from controlled alcohol/water solvent ratios. The key step, a heterocyclization reaction, proceeds by N,N-bond formation and delivers the 2H-indazole scaffold. Automated preparative HPLC was utilized to provide pure compounds on a 10+ mg scale.     

Positional assignment of differentially substituted bisaminoacylated pdCpAs

The synthesis and NMR analysis of a 2'-O-alanyl, 3'-O-[1-(13)C]valyl-pdCpA derivative has permitted the definitive assignment of the positions of acylation of tandemly activated pdCpAs, and the bisaminoacylated transfer RNAs derived therefrom.     

(+)-Myristinin A, a naturally occurring DNA polymerase beta inhibitor and potent DNA-damaging agent

The first stereoselective total synthesis of the naturally occurring flavan myristinin A has been accomplished, as well as its biochemical evaluation. This synthesis verified the structural assignment and allowed for the determination of the absolute stereochemistry. Myristinin A exhibits biochemical activity both as a potent DNA-damaging agent and DNA polymerase beta inhibitor. Relaxation of supercoiled plasmid DNA was observed at picomolar concentrations, in addition to inhibition of polymerase beta at low micromolar concentrations.     

Polyurethane-pyridylazonaphthol foams in the preconcentration and separation of trace elements

The feasibility of using PAN—polyether and polyester polyurethane foams in batch and column operations has been examined. The effects of pH, plasticizer and various anions present in the aqueous solution on the extraction behaviour of cobalt, iron and manganese have been investigated. In dynamic systems, the effect of flow rate on the extraction efficiencies of these metal ions has been investigated. The uptake of cobalt(III) and manganese(II) on PAN—polyester foam columns is quantitative at flow rates up to 10 ml min^-1 and 2 ml min^-1, respectively. The retention of iron(III) by the foam column is not quantitative even at a flow rate of 1 ml min^-1. Preconcentration of cobalt and its separation from various concentrations of manganese are successful..     

Total synthesis of quinolizidine alkaloid (-)-217A. Application of iminoacetonitrile cycloadditions in organic synthesis

[reaction: see text] An intramolecular iminoacetonitrile [4 + 2] cycloaddition functions as the key step in an efficient total synthesis of the quinolizidine alkaloid (-)-217A.     

Five-Step Enantioselective Synthesis of Islatravir via Asymmetric Ketone Alkynylation and an Ozonolysis Cascade

A 5-step enantioselective synthesis of the potent anti-HIV nucleoside islatravir is reported. The highly efficient route was enabled by a novel enantioselective alkynylation of an α,β-unsaturated ketone, a unique ozonolysis-dealkylation cascade in water, and an enzymatic aldol-glycosylation cascade.     

Hecke Algebras of Group Extensions

Abstract

We describe the Hecke algebra ?(Γ,Γ₀) of a Hecke pair (Γ,Γ₀) in terms of the Hecke pair (N,Γ₀) where N is a normal subgroup of Γ containing Γ₀. To do this, we introduce twisted crossed products of unital *-algebras by semigroups. Then, provided a certain semigroup S ? Γ/N satisfies S ^?1 S = Γ/N, we show that ? (Γ,Γ₀) is the twisted crossed product of ? (N,Γ₀) by S. This generalizes a recent theorem of Laca and Larsen about Hecke algebras of semidirect products.