Derivatives of 3-Deoxy-3-(N-Hydroxyamino)-D-Ribose

Abstract

A series of 3-(N-arylmethyl-N-hydroxyamino)-l,2-O-cyclopentylidene-3-deoxy-5-O-toluoyl-α-D-riboses has been prepared. The blocking groups used were chosen to allow an easy nucleosidation of these compounds to spin labelled analogs of natural nucleosides. The conformational behavior of the N-arylmethyl-N-hydroxyamino group has been studied using ³/_CH NMR coupling data and molecular mechanics computations. Upon spontaneous oxidation, these hydroxylamines led to the corresponding aminoxyl free radicals which were submitted to EPR spectroscopy and quantum mechanical computations at a semiempirical level (PM3).     

Synthesis of Sialyl Lewis X Analogues

Abstract

Sialyl Lewis X (SLe^x) analogs 2a and 2b were synthesised, where the N-acetyl-D-glucose and the D-galactose units of SLe^x 1 were replaced with an alkyl and a heteroalkyl spacer. Sulphate ester 6i was also synthesised from alcohol 6b and chlorosulphonic acid. A novel promoter, silver mercaptoethanesulphonate, was used to synthesise α-sialosides 2c. 7b and 7c.     

In celebration of 30 years of Structural Chemistry: a “delocalized” special issue

Structural Chemistry -     

Some aspects of the living isobutylene polymerization

The possibilities of increasing the livingness in cationic isobutylene polymerizations has been investigated. It has been assumed that the living chain-end is polarized but non-dissociated and relatively stable, therefore, i) shifting of the dissociation equilibrium by adding salts with common or non-common anion in excess, and ii) increasing of the stability of the chain-end by complexing it with electrondonors, may increase the livingness of the system. Indeed, the addition of n-Bu₄NCl or n-Bu₄NI to systems with BCl₃ or TiCl₄ coinitiators, as well as the addition of dimethyl sulphoxide as electrondonor in a broad concentration range, improved the living character. The possibility of complexation of the chain-end by the monomer has also been supported     

A Multicolumn Ion Chromatographic Determination of Nitrate and Sulfate in Waters Containing Humic Substances

Abstract

A three-column ion chromatographic system for the removal of humic substances from natural waters, and subsequent on-line concentration and determination of nitrate and sulfate using non-suppressed ion chromatography is presented. Humic substances are removed using disposable adsorption columns packed with chemically bonded amine silica material. The sample is directly transfered to an ion exchange column where the anions are concentrated ca 10 times. After reversing the flow, the ions are transferred to a third column where they are separated and quantified. The detection limit is less than 1 mg L^?1 of nitrate or sulfate in water containing 45mgL^?1 of humic acid.     

E. Thomas Strom and Vera V. Mainz (eds): The posthumous Nobel Prize in chemistry. Volume 1. Correcting the errors and oversights of the Nobel Prize committee

Structural Chemistry -     

Populations of coupled electrochemical oscillators

Experiments were carried out on arrays of chaotic electrochemical oscillators to which global coupling, periodic forcing, and feedback were applied. The global coupling converts a very weakly coupled set of chaotic oscillators to a synchronized state with sufficiently large values of coupling strength; at intermediate values both intermittent and stable chaotic cluster states occur. Cluster formation and synchronization were also obtained by applying feedback and forcing to a moderately coupled base state. The three cases differ, however, in other details. The feedback and forcing also produce periodic cluster states and more than two clusters. Configurations of two (chaotic) clusters and two, three, or four (periodic) clusters were observed. (c) 2002 American Institute of Physics.     

Kinetics and mechanism of the oxidation of sulfite by chlorine dioxide in a slightly acidic medium

The sulfite-chlorine dioxide reaction was studied by stopped-flow method at I = 0.5 M and at 25.0 +/- 0.1 degrees C in a slightly acidic medium. The stoichiometry was found to be 2 SO(3)(2-) + 2.ClO(2) + H(2)O --> 2SO(4)(2) (-) + Cl(-) + ClO(3)(-) + 2H(+) in *ClO(2) excess and 6SO(3)(2-) + 2*ClO(2) --> S(2)O(6)(2-) + 4SO(4)(2-) + 2Cl(-) in total sulfite excess ([S(IV)] = [H(2)SO(3)] + [HSO(3)(-)] + [SO(3)(2-)]). A nine-step model with four fitted kinetic parameters is suggested in which the proposed adduct *SO(3)ClO(2)(2-) plays a significant role. The pH-dependence of the kinetic traces indicates that SO(3)(2-) reacts much faster with *ClO(2) than HSO(3)(-) does.     

A scalable Nenitzescu synthesis of 2‐methyl‐4‐(trifluoromethyl)‐1H‐indole‐5‐carbonitrile

2‐Methyl‐4‐(trifluoromethyl)‐1H‐indole‐5‐carbonitrile is a key intermediate in the synthesis of selective androgen receptor modulators discovered in these laboratories. A practical and convergent synthesis of the title compound starting from 4‐nitro‐3‐(trifluoromethyl)phenol and tert‐butyl acetoacetate was developed, including a telescoped procedure for synthesis (without isolation) and Nenitzescu reaction of 2‐trifluoromethyl‐1,4‐benzoquinone. Conversion of the known Nenitzescu indole product to a novel triflate intermediate followed by palladium‐catalyzed cyanation afforded a penultimate carbonitrile. Removal of the C‐3 tert‐butyl ester group on the indole through a decarboxylative pathway completed the synthesis of the title compound in six steps (27% overall yield) from 4‐nitro‐3‐(trifluoromethyl)phenol (five steps, 37% overall yield from tert‐butyl acetoacetate). J. Heterocyclic Chem., (2011).     

Structures and mechanisms in chemical reactions: George A. Olah’s life-long search of chemistry

The Hungarian-born American chemistry Nobel laureate George A. Olah used superacids to give longer life to carbocations. He resolved a long-standing debate on reaction mechanism in organic chemistry and, more importantly, opened new vistas in hydrocarbon chemistry to produce hosts of new compounds. The concerted utilization of organic synthesis, physical techniques, and computational methods led to spectacular achievements in hydrocarbon chemistry. Olah has always been on the lookout for the practical applications of his discoveries in fundamental chemistry. He continued his research after his Nobel award and has worked out the idea, which he labeled “the methanol economy.” Olah’s example shows that a great researcher can also be a devoted and caring human being.