Copper-catalyzed annulative amination of ortho-alkynylphenols with hydroxylamines: synthesis of 3-aminobenzofurans by umpolung amination strategy

A room temperature copper-catalyzed annulative amination of ortho-alkynylphenols with electrophilic amination reagents, O-acylated hydroxylamines, proceeds efficiently to provide the corresponding 3-aminobenzofurans of biological and pharmaceutical interest.     

Copper-catalyzed direct sulfoximination of azoles and polyfluoroarenes under ambient conditions

The direct dehydrogenative C-N coupling of azoles or polyfluoroarenes with N-H sulfoximines proceeds effectively in the presence of a copper catalyst at room temperature under air to afford the corresponding N-arylsulfoximines in good to high yields.     

Brownian dynamics simulations with spin Brownian motion on the negative magneto-rheological effect of a rod-like hematite particle suspension

We have investigated the behaviour of a suspension of magnetic rod-like hematite particles in a simple shear flow with the addition of an applied magnetic field. A significant feature of the present hematite particle suspension is the fact that the magnetic moment of the hematite particle lies normal to the particle-axis direction. From simulations, we have attempted to clarify the dependence of the negative magneto-rheological effect on the particle aggregation and orientational distribution of particles. The present Brownian dynamics method has a significant advantage in that it takes into account the spin rotational Brownian motion about the particle axis in addition to the ordinary translational and rotational Brownian motion. The net viscosity is decomposed into three components and discussed at a deeper level and in detail: these three viscosity components arise from (1) the torque due to the magnetic particle–field interaction, (2) the torque and (3) the force due to the interaction between particles. It is found that a slight change in the orientational distribution has a significant influence on the negative magneto-rheological effect. In a relatively dense suspension, the viscosity components arising from an applied magnetic field and the interaction between particles come to change rapidly for a certain strength of the magnetic particle–particle interaction, which is due to the onset of the formation of raft-like clusters.     

Practical synthesis of a neuropeptide Y antagonist via stereoselective addition to a ketene

[Reaction: see text]. The synthesis of neuropeptide Y antagonist 1, currently under clinical investigation for the treatment of obesity, is described. The convergent synthesis from trans-spirolactone carboxylic acid intermediate 2a and aminopyrazole 3 is predicated on a stereoselective route to the former. The coupling reaction of ethyl 4-oxocyclohexanecarboxylate (10a) with lithiated isonicotinamide 11 was investigated in detail, but even optimized conditions only provided a 45:55 ratio of trans:cis isomers (12a:12b). While selective crystallization schemes were developed to isolate the thermodynamically less stable trans isomer 2a, improved stereocontrol was subsequentially achieved by the application of ketene chemistry. The ketene formation and quench was investigated under a variety of conditions aimed at maximizing the trans:cis ratio. Reacting a mixture of carboxylic acids 2a and 2b with POCl3 in THF, followed by concomitant addition of tert-butyl alcohol in the presence of TMEDA at 35 degrees C provided a 4:1 ratio of trans:cis tert-butyl esters (18a:18b) via in situ ketene formation. Ester hydrolysis, followed by selective crystallization of undesired 2b as the HCl salt, led to isolation of 2a in 47% overall yield. Aminopyrazole intermediate 3 was synthesized via the condensation reaction of 2-fluorophenylhydrazine hydrochloride (4a) with acrylonitrile derivative 5 in 65-70% yield. Coupling of advanced intermediates 2a and 3b via activation with thionyl chloride gave a 92% yield of 1.     

A lower bound for the number of Reidemeister moves of type III

We study the number of Reidemeister type III moves using Fox n-colorings of knot diagrams.     

Metal‐cation‐induced chiroptical switching for poly(phenylacetylene) bearing a macromolecular ionophore as a graft chain

A poly(phenylacetylene) bearing a polycarbohydrate ionophore as a graft chain (copolymer 4 ) was synthesized by the copolymerization of end‐functionalized (1→6)‐2,5‐anhydro‐3,4‐di‐O‐ethyl‐D ‐glucitol with a 4‐ethynylbenzoyl group (macromonomer 2 ) with phenylacetylene. Copolymer 4 showed a split‐type circular dichroism (CD) in the long absorption region of the conjugated polymer backbone (280–500 nm), and the CD pattern varied in response to external stimuli, such as the solvents and temperature. This suggested that 4 had a predominantly one‐handed helical conformation in the polyacetylene backbone. The CD pattern of 4 was completely inverted by the formation of a complex between the macromolecular ionophore units and the selected metal cations, that is, Ba²⁺, Pb²⁺, Sr²⁺, Na⁺, and Li⁺. This suggested that copolymer 4 underwent a helix–helix transition through the host–guest complexation with achiral inorganic metal cations. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5855–5863, 2005     

Studies on the syntheses of heterocyclic compounds. Part DCXLIV . Catalytic reduction of homoproaporphine related compounds

Hydrogenation of the homoproaporphine (IV) over platinum oxide gave a mixture of the cyclohexanols VIIa and VIIb. In contrast, reduction of IV on palladium provided the cyclo-hexanone VI, which was also obtained from VIIb by oxidation. Treatment of the cyclohexanols VIIa and VIIb under hydrogen on platinum oxide afforded the same mixture of VIIa and VIIb.     

1-Phosphacephalosporin. I. Synthesis of racemic 7-unsubstituted-1-phosphadethia-3-cephem 1-oxides

The novel unnatural ring system, 1-phosphacephalosporin, was synthesized for the first time from 4-acetoxy-2-azetidinone.