Enantioselective construction of triaryl-substituted all-carbon quaternary stereocenters via organocatalytic arylation of oxindoles with azonaphthalenes.

Azonaphthalenes have been verified as a class of effective arylation reagents in a variety of asymmetric transformations. Here a highly efficient approach to construct triaryl-substituted all-carbon quaternary stereocenters through chiral phosphoric acid-catalyzed enantioselective arylation of 3-aryl-2-oxindoles with azonaphthalenes is disclosed. This chemistry is scalable and displays excellent functional group tolerance, furnishing a series of 3,3-disubstituted 2-oxindole derivatives in good yields with excellent enantiocontrol. Preliminary mechanistic data suggest that the initially formed direct addition intermediate undergoes intramolecular annulation under acidic reaction conditions.

DNA-binding and photoactivated enantiospecific cleavage of chiral polypyridyl ruthenium(II) complexes.

A series of enantiomeric polypyridyl ruthenium(II) complexes Delta- and Lambda-[Ru(bpy)2CNOIP](PF6)2 (Delta-1 and Lambda-1; BPY=2,2'-bipyridine, CNOIP=2-(2-chloro-5-nitrophenyl)imidazo[4,5-f][1,10]phenanthroline), Delta- and Lambda-[Ru(bpy)2HPIP](PF6)2 (Delta-2 and Lambda-2; HPIP=2-(2-hydroxyphenyl)imidazo[4,5-f][1,10]phenanthroline), Delta- and Lambda-[Ru(bpy)2DPPZ](PF6)2 (Delta-3 and Lambda-3; DPPZ=dipyrido[3,2:a-2',3':c]-phenazine), Delta- and Lambda-[Ru(bpy)2TAPTP](PF6)2 (Delta-4 and Lambda-4; TAPTP=4,5,9,18-tetraazaphenanthreno[9,10-b] triphenylene) have been synthesized. Binding of these chiral complexes to calf thymus DNA has been studied by spectroscopic methods, viscosity, and equilibrium dialysis. The experimental results indicated that all the enantiomers of these complexes bound to DNA through an intercalative mode, but the binding affinity of each chiral complex to DNA was different due to the different shape and planarity of the intercalative ligand. After binding to DNA, the luminescence property of complex 1 was distinctly different from complexes 2 to 4. Upon irradiation at 302 nm, complexes 2-4 were found to promote the cleavage of plasmid pBR 322 DNA from supercoiled form I to nicked form II, and obvious enantioselectively was observed on DNA cleavage for the enantiomers of complexes 2 and 4. The mechanisms for DNA cleavage by these enantiomeric complexes were also proposed.

A functionalized cobalt(III) mixed-polypyridyl complex as a newly designed DNA molecular light switch.

The ligand ODHIP (3,4-dihydroxyl-imidazo[4,5-f][1,10]phenanthroline) and its cobalt(III) complex [Co(bpy)(2)(ODHIP)](3+) were synthesized and characterized. Binding of this complex with calf thymus DNA has been investigated by spectroscopic methods and viscosity. The experimental results indicated that the complex bound to DNA by intercalation. In Tris buffer, the complex could emit relatively weak luminescence. After binding to DNA, the notable enhancement was observed. However, when the Cu(2+) was further added, the luminescence decreased gradually and disappeared after the equimolar concentrations of Cu(2+) was added, which exhibited the "off-on-off" properties of molecular light switch.