Mechanism of cleaving DNA through hydrolysis of a novel complex of Mg containing dien ligand

A series of metal complexes were designed and synthesized and a novel binuclear magnesium complex has been selected, namely [Mg-2(dien)Cl(OH2)(2)]Cl-2 . H2O (dien=diethylene-triamine), which can cleave the plasmid pBR322 DNA effectively in close to physiological condition without adding any external materials. Through biological and chemical methods, especially the comparative experiments, we find the interaction between the complex and DNA belongs to hydrolytic mechanism.

Rhodium-Catalyzed Asymmetric Trifluoromethoxylation of Racemic Allylic Trichloroacetimidates

A rhodium/diene catalyzed asymmetric allylic trifluoromethoxylation reaction is reported,which afforded chiral trifluoromethoxylated allylic compounds in 52%–97%yields with up to 97%enantiomeric excess.These are the first examples of asymmetric allylic trifluoromethoxylation.The reactions proceed via a dynamic kinetic process that allowed for the use of racemic allylic trichloroacetimidates as substrates.Density functional theory calculations showed that the formation of the C–OCF_(3)bond occurs via outer-sphere nucleophilic attack.Importantly,the presence of the allylic group in the products enabled them to be converted into a diverse array of optically active trifluoromethylated molecules that are otherwise difficult to access.

Rhodium catalyzed asymmetric synthesis of Chiraphos derivatives

Herein,we report a highly efficient versatile synthetic route to Chiraphos derivatives through Rh/Ph-bod catalyzed asymmetric addition of aryl boronic acids to phosphinyl dienes.Various substituted phosphinyl dienes,both on the parent skeleton and the phosphine atoms,were well tolerated with this method and provided chiral phosphine oxides in satisfied yield and up to 95%ee.The corresponding Chiraphos derivative displayed an advantage over Chiraphos in the representative Pd-catalyzed asymmetric 1,4-addition reaction.