Palladium‐Catalyzed C−H Iodination of Arenes by Means of Sulfinyl Directing Groups

C?H iodination of aromatic compounds has been accomplished with the aid of sulfinyl directing groups under palladium catalysis. The reaction proceeds selectively at the peri‐position of polycyclic aryl sulfoxides or at the ortho‐position of phenyl sulfoxides. The iodination products can be further converted via iterative catalytic cross‐coupling at the expense of the C?I and C?S bonds. Computational studies suggest that peri‐C?H palladation would proceed via a non‐directed pathway, wherein neither of the sulfur nor oxygen atom of the sulfinyl group coordinates to the palladium before and at the transition state.     

Lembehsterols A and B,novel sulfated sterols inhibiting thymidine phosphorylase,from the marine sponge Petrosia strongylata

Lembehsterols A (1) and B (2), two novel sulfated sterols, were isolated from the marine sponge Petrosia strongylata. Both sterols showed inhibitory activity against thymidine phosphorylase, which is an enzyme related to angiogenesis in solid tumors. The structures of these sulfated sterols were established on the basis of chemical and physicochemical evidence.     

C-S bond cleavage of pyridine-2-thiol: a new functionality of quadruply bridged dinuclear platinum and palladium complexes

Treatment of pyridine-2-thiol (pytH) with H(2) (60 atm) in the presence of 5-methylpyridine-2-thiolate (5-mpyt)-bridged dinuclear Pt(III), Pt(II), or Pd(II) complexes (1 mol %) in DMF at 150 degrees C for 72 h leads to the formation of pyridine in 3-51% yield. From the (1)H NMR study of the exchange reactions and of the products under D(2) pressure, it is suggested that the catalytic reaction involves bimetallic activation of the pyt ligand followed by the liberation of pyridine and H(2)S.     

Selective absorption

Summary Some organic acids, alcohol and amine which have an asymmetric carbon atom were used for an investigation of asymmetric absorption on wool. Racemic mixture of hydratropic acid, mandelic acid andα-phenethylamine have shown the selective absorption on wool from their aqueous and alcoholic aqueous solutions and S-form of their diastereoisomers preferentially absorbed on wool. According to the results we obtained so far, it is concluded that the preferential absorption strongly depends on the configuration of the substance of which wool is composed.     

Alternating cooligomerization of isoprene and propylene with vanadium catalyst

Alternating cooligomerization of isoprene with propylene has been investigated between ?30 and 0°C, VO(acac)₂–Et₃Al–Et₂AlCl being used as catalyst. In the presence of an excess of propylene, 2,4,7-trimethyl-1,4-octadiene and 2,4-dimethyl-1,4-nonadiene are selectively formed. The formation is explained by the alternating coordination of isoprene and propylene to the vanadium. When triphenylphosphine or pyridine is added to the catalyst, the cooligomerization is suppressed while the formation of the dimer and trimer of isoprene is high.