1. Highly ordered mesoporous polymer-supported phosphine as the ligand for organometallic reactions.

Abstract

1. Development of highly reactive and selective transition metal catalyst is the one of the main discipline in modern organic chemistry. In general, the formation of mono-ligated Pd(0)-L species is believed to be important for active catalyst, and this coordinatively unsaturated catalyst enables the cross-coupling of inactivated molecules in mild condition. These kinds of reactive catalysts, however, are commonly air- and moisture-sensitive and high-cost privileged ligand was required. Herein, our group envisioned the highly-ordered mesoporous polymer-supported simple phosphine generating mono-ligated Pd(0)-L species and achieved the Suzuki cross-coupling of aryl chlorides at room temperature. In addition, we also prepared rigid macroporous polymer-supported phosphine, and then demonstrated the successful Suzuki cross-coupling of both aryl chlorides and sterically hindered aryl bromides at room temperature. We expect this catalytic system involving polymer-supported phosphine could provide not only novel reactivity and but also potential for various organometallic reactions. 2. Constructing complex structure of polycyclic compound is important topic in organic synthesis. Among them, [3+2] Cycloaddition is widely used in organic chemistry to increase the structural complexity efficiently. Recently, 1-sulfony-1,2,3-triazole got attention as the readily available precursor of α-iminocarbenoid, having strong electrophilicity that can proceed many useful transformations, in the presence of the rhodium catalyst. Our group realized that the carbonyl ylide could generated from adjacent carbonyl group with $\alpha$-iminocarbenoid, and proceeded stereoselective [3+2] cycloaddition with intramolecular olefin. We also varied the ring-size of carbonyl ylide and the length of olefin chain, and then provided various type of oxygen-bridged polycyclic compounds which are observed as core structures in various natural products.