A highly chemoselective oxidation of alcohols to carbonyl products with iodosobenzene diacetate mediated by chromium(III)(salen) complexes: synthetic and mechanistic aspects

[reaction: see text] The catalytic oxidation of the allylic alcohols 1d-n with iodosobenzene diacetate, mediated by the [Cr(III)(salen)]X complex, affords the respective enones in excellent chemoselectivity for Cl(-) as counterion [complex A(Cl)], while for the counterions TfO(-) [complex A(TfO)] and PF(6)(-) [complex A(PF(6)())] nearly equal amounts of enone and epoxide are observed. This counterion-dependent oxidation of allylic alcohols by Cr(III)(salen) complexes is rationalized in terms of Lewis acid catalysis by the complex A(Cl) and redox catalysis for A(TfO) and A(PF(6)()).     

Use of allylzinc halide as a source of halide: Differential addition of nucleophiles to Ts-aziridines and aldehydes under similar reaction conditions

We have observed that the allylic zinc halide under identical reaction conditions acts in different modes for different electrophiles. For Ts-aziridines the halide part of the allylic halide has been introduced as a nucleophile and for the carbonyl compounds the simple allylation reaction occurs. To the best of our knowledge this is the first report where the allylic zinc halide is the source of halide acting as nucleophile. The main advantages of the present procedure are easy to handle, no need of inert atmosphere, mild reaction conditions, and applicability to a wide variety of substrates for aziridines and carbonyl compounds.     

Recent advances on heterocyclic compounds with antiviral properties

Chemistry of Heterocyclic Compounds - In recent years several important viral infections have emerged and antiviral chemotherapeutic agents are not sufficiently effective in clinic, leading to...     

Catalytic enantioselective synthesis of A-86929, a dopamine D1 agonist

A-86929, a dopamine D1 agonist was synthesized with 95% ee in five steps with overall yield of 56% via catalytic enantioselective one-pot aziridination followed by Friedel-Crafts cyclization and a mild Pictet-Spengler cyclization protocol.     

Visible-light-promoted oxidative coupling of styrene with cyclic ethers

A new visible-light-promoted oxidative coupling of vinylarenes with cyclic ethers has been developed using rose bengal as photocatalyst and tert-butyl hydrogenperoxide(TBHP) as oxidant under ambient air at room temperature. A library of α-oxyalkylated ketones with broad functionalities has been synthesized in moderate to good yields. A radical mechanism is suggested for the present protocol.     

Zinc-Ion-Induced Aggregation of Gold Clusters for Visible-Light-Excitation-Based Fluorimetric Discrimination of Geometrical Isomers

Herein, we report discrimination of dicarboxylic acids – fumaric acid (FA) and maleic acid (MA) – exhibiting geometrical isomerism, using nanoclusters based luminescent probe having excitation under broad day light. The luminescent probe was designed via complexation reaction between zinc ions and ligands (mercaptopropioinc acid; MPA) stabilizing the gold nanoclusters. This resulted in formation of nanoaggregates exhibiting bright green luminescence upon excitation at 450 nm capable of discriminating between FA and MA upto nanomolar level. The basis of discrimination has been attributed to deprotonation of FA and MA following interaction with MPA moieties present on the surface of the nanoaggregates and being governed by the stability of the respective conjugate base of the geometrical isomers of the dicarboxylic acids. As a consequence of different extent of deprotonation of FA and MA upon interaction with the cluster aggregates, different effect on the luminescence of the aggregates was observed, thus enabling discernible fluorimetric discrimination between FA and MA under visible light excitation.     

Classical interpretations of relativistic precessions

Relativists have exposed various precessions and developed ingenious experiments to verify those phenomena with extreme precisions. The Gravity Probe B mission was designed to study the precessions of the gyroscopes rotating round the Earth in a nearly circular near-Earth polar orbit to demonstrate the geodetic effect and the Lense-Thirring effect as predicted by the general relativity theory. In this paper, we show in a very simple and novel analysis that the precession of the perihelion of Mercury, the Thomas precession, and the precession data （on the de Sitter and Lense-Thirring precessions） collected from the Gravity Probe B mission could easily be explained from classical physics, too.     

Aminohydroxyphosphine ligand for the copper-catalyzed enantioselective conjugate addition of organozinc reagents

An alanine-derived aminohydroxyphosphine ligand was developed for copper-catalyzed asymmetric conjugate addition of organozinc reagents to alpha,beta-unsaturated carbonyl compounds. This new tridentate ligand induces consistently high enantioselectivity in reactions of a variety of acyclic substrates. Theoretical mechanistic analysis suggests that the C-C bond formation takes place through a highly ordered transition state by the coordination of the phosphorus and nitrogen atoms to the copper(III) and zinc(II) atoms, respectively, and of the oxygen anion to both the metal centers.     

Formylation without catalyst and solvent at 80 °C

A simple and efficient protocol for N-formylation of aliphatic and heterocyclic amines has been described with formic acid in the absence of catalyst and solvent.