Unusual Catalytic Effect of the Two-Dimensional Molecular Space with Regular Triphenylphosphine Groups

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• 作者：Chen Chen ; Xue Shao ; Ken Yao ; Jian Yuan ; Wenfeng Shangguan ; Toshikazu Kawaguchi ; Katsuaki Shimazu
• 刊名：Langmuir
• 出版年：2011
• 出版时间：October 4, 2011
• 年：2011
• 卷：27
• 期：19
• 页码：11958-11965
• 全文大小：916K
• 年卷期：v.27,no.19(October 4, 2011)
• ISSN：1520-5827

文摘

A novel organic鈥搃norganic hybrid 2D molecular space with regular triphenylphosphine groups (triphenylphosphineamidephenylsilica, PPh₃APhS) 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 PPh₃APhS. The catalytic potentials of 2D molecular space with regular triphenylphosphine groups were investigated. An unusual catalytic effect was found in a carbon鈥損hosphorus ylide reaction. The PPh₃-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 PPh₃APhS. 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 PPh₃APhS. 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.