890127-34-1Relevant articles and documents
Synthesis of polymer-immobilized TsDPEN ligand and its application in asymmetric transfer hydrogenation of cyclic sulfonimine
Sugie, Haruki,Hashimoto, Yosuke,Haraguchi, Naoki,Itsuno, Shinichi
, p. 711 - 716 (2014)
Crosslinked polymers containing chiral N-sulfonylated diamine (TsDPEN) structure were synthesized by radical polymerization of chiral N 1-(4-vinylbenzenesulfonyl)-1,2-diphenylethylene-1,2-diamine, divinylbenzene and achiral vinyl monomer. The p
Preparation and catalytic performances of a molecularly imprinted RU-complex catalyst with an NH2 binding site on a SiO2 surface
Yang, Yong,Weng, Zhihuan,Muratsugu, Satoshi,Ishiguro, Nozomu,Ohkoshi, Shin-Ichi,Tada, Mizuki
experimental part, p. 1142 - 1153 (2012/03/26)
A catalyst surface with an active metal site, a shape-selective reaction space, and an NH2 binding site for o-fluorobenzophenone was designed and prepared by the molecular imprinting of a supported metal complex on a SiO2 surface. A ligand of a SiO2-supported Ru complex that has a similar shape to the product of o-fluorobenzophenone hydrogenation was used as a template. An NH2 binding site for o-fluorobenzophenone was spatially arranged on the wall of a molecularly imprinted cavity with a similar shape to the template. The structures of the SiO2-supported and molecularly imprinted Ru catalysts were characterized in a step-by-step manner by means of solid-state magic angle spinning (MAS) NMR, XPS, UV/Vis, N 2 adsorption, XRF, and Ru K-edge EXAFS. The molecularly imprinted Ru catalyst exhibited excellent shape selectivity for the transfer hydrogenation of benzophenone derivatives. It was found that the NH2 binding site on the wall of the molecularly imprinted cavity enhanced the adsorption of o-fluorobenzophenone, of which the reduction product was imprinted, whereas there was no positive effect in the case of o-methylbenzophenone, which cannot interact with the NH2 binding site through hydrogen bonding. Tailoring a pocket: A molecularly imprinted Ru-complex catalyst with an NH 2 binding site for o-fluorobenzophenone has been successfully designed and prepared on a SiO2 surface for shape-selective transfer hydrogenation (see scheme). Copyright
Synthesis of polymer microspheres functionalized with chiral ligand by precipitation polymerization and their application to asymmetric transfer hydrogenation
Haraguchi, Naoki,Nishiyama, Akihiro,Itsuno, Shinichi
experimental part, p. 3340 - 3349 (2011/04/26)
Monodisperse, crosslinked poly(divinylbenzene) and poly(methacrylic acid-co-ethylene glycol dimethacrylate) microspheres with (1R,2R)-N 1-toluenesulfonyl-1,2-diphenylethylene-1,2-diamine ((R,R)-TsDPEN) moiety were successfully prepared by precipitation polymerization. Introduction site of the (R,R)-TsDPEN moiety into the polymer microspheres could be controlled by changing the order of addition of the corresponding monomers. The functionalized polymer microspheres were applied to asymmetric transfer hydrogenation of ketone and imine. Polymer microsphere-supported chiral catalysts showed good reactivity and enantioselectivity in the catalytic asymmetrie transfer hydrogenations. Chiral secondary alcohol was quantitatively obtained with 94% ee in the asymmetric transfer hydrogenation of acetophenone in water. We also found that introduction site of the chiral catalyst and hydrophobiclty of the microspheres, as well as degree of the crosslinking, affected the yield and enantioselectivity of chiral product in this reaction.
