title: Unusual catalytic effect of the two-dimensional molecular space with regular triphenylphosphine groups.
abstract: A novel organic-inorganic hybrid 2D molecular space with regular triphenylphosphine groups (triphenylphosphineamidephenylsilica, PPh(3)APhS) was successfully synthesized through grafting triphenylphosphine groups in the 2D structure of layered aminophenylsilica dodecyl sulfate (APhTMS-DS), which was developed in our previous research, with regular ammonium groups. The 2D structures were kept after the grafting reaction of triphenylphosphine groups in PPh(3)APhS. The catalytic potentials of 2D molecular space with regular triphenylphosphine groups were investigated. An unusual catalytic effect was found in a carbon-phosphorus ylide reaction. The PPh(3)-catalyzed reaction of modified allylic compounds, including bromides and chlorides with tropone yielded a [3 + 6] annulation product. However, an unusual [8 + 3] cycloadduct was obtained in the reaction of modified allylic compounds, including bromides and chlorides with tropone catalyzed by PPh(3)APhS. Otherwise, the stable catalytic intermediate was successfully separated, and the reaction activity of the catalytic intermediate was confirmed in the reaction of modified allylic compounds with tropone catalyzed by PPh(3)APhS. This research is the first successful example of directly influencing catalytic reaction processes and product structures by utilizing the chemical and geometrical limits of 2D molecular spaces with regular catalyst molecules and affords a novel method for controlling catalytic reaction processes and catalyst design.
authors: Department of Chemistry, Shanghai University, Shanghai 200444, PR China.
authors: Chen
authors: C
authors: Chen
authors: Xue
authors: X
authors: Shao
authors: Ken
authors: K
authors: Yao
authors: Jian
authors: J
authors: Yuan
authors: Wenfeng
authors: W
authors: Shangguan
authors: Toshikazu
authors: T
authors: Kawaguchi
authors: Katsuaki
authors: K
authors: Shimazu
mesh_terms: D002384:Catalysis; D015394:Molecular Structure; D009943:Organophosphorus Compounds / Q000737:chemistry*; D017646:Organosilicon Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D012822:Silicon Dioxide / Q000737:chemistry*
chemical_list: D009943:Organophosphorus Compounds; D017646:Organosilicon Compounds; C061896:triphenylphosphine; D012822:Silicon Dioxide