Catalyst Design Based on Functionalized Phosphines with a Compact Coordination Center

1.笼状膦SMAP的研究改进了各种SMAP衍生物的母体化合物Ph-SMAP的合成工艺。结果表明，Ph-SMAP是一种优良的酮硅氢加成和水合配体。所得到的SiO_2-SMAP对Rh催化的硅氢化反应和高位阻的酮的氢化反应表现出很高的配位体性能。此外，SiO_2-SMAP还被成功地用于发展Ir催化的官能化芳烃的定向邻位硼化反应。所制备的Au-SMAP在Rh催化的脱氢醇硅化反应中表现出显著的高活性和转化效率。半中空三炔基膦的研究合成了不同端基的三乙炔基膦配体。具有较大端基的化合物表现出独特的配位性能，可以选择性地与各种过渡金属物种形成1：1的金属-膦配合物。在Rh催化的酮硅氢加成反应中，半中空形状的三乙炔基膦表现出极高的加速作用。此外，半中空的三乙炔基膦被成功地用作金催化的乙炔环合反应的配体。其中，6-exo-dig和7-exo-dig环化的促进作用显著。此外，这一催化剂系统使内部的炔衍生物发生了前所未有的环化反应。

1. Research with Caged Phosphine SMAPThe procedure for the synthesis of Ph-SMAP, the parent compound for various SMAP derivatives, was improved. It was confirmed that Ph-SMAP is an excellent ligand for hydrosilylation and hydrgenation of ketones.SMAP was immobilized on silica gel surface. Silica-SMAP thus obtained showed very high ligand performance for the Rh-catalyzed hydrosilylation and hydrogenation of sterically demanding ketones.Furthermore, Silica-SMAP was successfully used for the development of Ir-catalyzed directed ortho borylation of functionalized arenes.SMAP derivatives bearing an alkanethiol pendant at the bridgehead silicon atom was prepared and used for the preparation of self-assembled monolayer on gold surface. Au-SMAP thus prepared showed remarkably high activity and turnover efficiency in the Rh-catalyzed dehydrogenative alcohol silylation.2. Research with Semihollow TrialkynylphosphinesTriethynylphosphine ligands with different end-cap groups were synthesized. Those with bulky end-caps showed unique coordination properties to form 1:1 metal-phosphine complexes selectively with various transition metal species. The semihollow-shaped triethynylphosphines showed extraordinally high accelerating effect in the Rh-catalyzed hydrosilylation of ketones. Furthermore, the semihollow triethynylphosphines were successfully used as ligands for gold-catalyzed alkyne cyclizations. In particular, the accelerating effect in the 6-exo-dig and 7-exo-dig cyclization was remarkable. In addition, this catalyst system enabled unprecedented cyclizations of internal alkyne derivatives.