Development of Gold-and Palladium-catalyzed New Transformations via Modification of Ligands

通过配体和反阴离子的修饰，发展了新型的Pd和Au催化的分子转化，表现出高的反应活性和选择性。合成了多种降冰片烷衍生物，并成功地应用于钯催化的不对称分子内氢胺化反应。新合成的(R，R)-甲基降冰片和(R，R)-甲苯基重构体提供了高产率和高对映体选择性的含氮杂环。此外，还开发了新型的钯催化烯丙化脱芳构化和三组分环加成反应。我们已经成功地开发了阳离子Au催化的氢烷氧基化和氢硫醇化反应。此外，我们还成功地通过一种新的Au催化的芳二炔的级联环化反应构建了噻吩咔唑骨架，并将其进一步应用于D-A-D有机电子材料的合成。通过简单有效的亲电碘化反应，合成了各种含O-、S和N-二碘取代的杂环化合物。

Novel Pd-and Au-catalyzed molecular transformations have been developed through the modification of ligands and counter anions which showed high reactivity and selectivity. A variety of Norbornane derivatives have been synthesized and successfully used in the Pd-catalyzed asymmetric intramolecular hydroamination of alkynes. The newly prepared (R, R)-methyl norphos and (R, R)-toly renorphos afforded N-containing heterocyles in high yields and high enantio-selectivity. Moreover, novel Pd-catalyzed allylative dearomatization and three-component cycloaddition were developed. We have succeeded in development of cationic Au-catalyzed hydroalkoxylation and hydrothiolation. Moreover, we also succeeded in construction of thienocarbazole frameworks via a new Au-catalyzed cascade cyclization of arydiynes, which was further applied in the synthesis of D-A-D organic electronic materials. Various O-, S-and N-containing heterocyles bearing diiodine substituents have been synthesized through the facile and efficient electrophilic iodocyclizations.