Development of Highly Efficient Organometallic Catalysis for Short-step Assembly of Complex Moleculer Structures

1.在催化量的Cp*Ru(Cod)Cl存在下，具有多种官能团的不对称1，6-二炔在酮C=0的双键上与缺电子的三酮化合物反应，通过预期的α-吡喃的电环开环选择性地生成二烯酮。Pd(0)催化的缺电子二炔和三炔的环化反应有效地合成了多环芳香族化合物。通过对相关中间体的表征和中间体模型的密度泛函计算，阐明了它们的反应机理。以乙二胺、β-不饱和酯和羟基硅烷为原料，采用一锅法合成α，β-氨基酯。在催化量的阳离子Ir络合物存在下，丙叉型乙酸酯很容易与烯氧基硅烷反应，生成β-炔基酮，产率高到很好。在大多数类型的炔丙酸酯中，丙炔基碳上的取代是排他地或选择性地进行的。或者，在酯的反应中，烯丙基产物的形成占主导地位，在炔丙基碳上有两个苯基。

1. In the presence of catalytic amounts of Cp*Ru(cod)Cl, unsymmetrical 1,6-diynes possessing a variety of functional groups reacted with electron-deficient tricarbonyl compounds at the ketone C=0 double bonds to selectively afford dienones via electrocyclic ring opening of the expected α-pyrans.2. The Pd(0)-catalyzed cyclization of electron-deficient diynes and triynes efficiently gave polycyclic aromatic coupounds. Their reaction mechanism was elucidated by means of the characterization of relevant intermediate complexes and density functional calculations of intermediate models.3. A rhodium-catalyzed method for the synthesis of β-amino esters was accomplished in a one-pot procedure from aldimine, α,β-unsaturated ester and hydosilane.4. Propargylic-type acetates react readily with enoxysilanes in the presence of a catalytic amount of a cationic iridium complex to give β-alkynyl ketones in high to excellent yields. Substitution at propargyl carbon proceeds exclusively or selectively in most types of propargylic esters. Alternatively, the formation of the allenyl products is predominant in the reaction of esters, which have two phenyl groups on the propargyl carbon.