三价钐催化的carbonyl-ene反应及其在有机合成中的应用研究

The carbonyl-ene reaction is an important reaction in organic synthesis. This type of reactions are able to atom-economically construct a wide range of functionalized cyclic products, and have been successfully applied in many elegant syntheses. However, most of carbonyl-ene reactions need stoichiometric amount of strong Lewis acids or Bronsted acids to complete the reactions, and few catalytic examples have been reported. Our recent research found that samarium triiodide (SmI3), an air-stable solid, could efficiently catalyze the carbonyl-ene reactions with good stereoseletivity. Furthermore, it could be scaled up and used to build a wide range of functionalized five-membered ring systems. Consdiering today's limited knowledge of utilizing catalytic amount of samarium(III), we plan to further study in this proposed project the Sm(III)-catalyzed carbonyl-ene reactions and its asymmetric version with the aid of chiral ligands, as well as the potential applications to the synthesis of bioactive natural products.

Carbonyl-ene反应是在有机化学中是一种重要的反应。 它能够原子经济性的够建复杂的环系产物,这在合成中有潜在的应用前景.然而大多数的 Carbonyl-ene反应需要化学计量的强路易斯酸或Bronsted酸来完成反应,催化的反应很少有报道.我们最近的研究发现三碘化钐(SmI3,在空气中稳定)能够高效的催化carbonyl-ene反应。另外,这个催化反应能够放大制备官能团化的五元环系产物.三价钐催化的反应一直研究的比较少,我们计划进一步研究三价钐在手性配体作用下催化的不对称Carbonyl-ene反应，并将这些结果应用于活性天然产物的合成。

Carbonyl-ene反应是在有机化学中是一种重要的反应。 它能够原子经济性的够建复杂的环系产物,这在合成中有潜在的应用前景.我们发现三碘化钐(SmI3)能够高效的催化carbonyl-ene反应形成官能团化的五元环系。我们研究了三价钐在手性配体作用下催化的Carbonyl-ene反应，并将这些结果应用于Hamigeranl类活性天然产物的合成研究中。在研究过程中我们发现了三碘化钐能够催化α-取代β-羰基酯和酰胺化合物的α-羟基化反应，进过文献检索发现多种天然产物和生物活性分子中含有此类结构单元.