Ruthenium Complex-Catalyzed Highly Selective Organic Syntheses

我们一直在研究Ru络合物催化的新型选择性有机合成，特别是从新型和选择性碳-碳键形成反应的角度进行研究。在本论文的工作中，我们发展了一种新的方法，即通过吡烯丙基Ru络合物作为关键中间体或甲酰基C-H键活化来构建碳骨架，以及使用相关的过渡金属络合物催化剂进行选择性有机合成。今年，我们发现了几种ETA^3-烯丙基Ru(II)配合物，如(ETA^3-烯丙基)Ru(OAc)(CO)_3或阳离子(ETA^3-烯丙基)Ru(CO)_3]^+(OTf)^-，既可以作为亲核试剂，也可以作为亲电试剂。2.发展了Ru络合物催化的烷基甲酸酯的新型转化反应：甲酸烷基酯选择性脱羰制醇、中性介质中烷基甲酸酯与芳烃和烯烃的烷基化反应以及醇与烯烃的加成反应。3.在7族和8-10族金属羰基催化剂，包括Ru络合物存在下，烷基碘的光、电和热羰基化反应。4.在Ru络合物催化反应的研究过程中，我们发现在CO_2(CO)_8催化的环氧乙烷和环氧乙烷在常温、一氧化碳气氛下的开环羰基化反应具有很高的区域选择性，分别高产率地得到了相应的β-和γ-硅氧酰胺。此外，PdCl2(PPh_3)_2-SnCl2体系对硝基苯还原N-杂环化成吲哚和2H-吲唑衍生物具有很高的催化活性。在PdCl2(PPh3)2和MoCl5的作用下，2-硝基苯甲醛或2-硝基苯酮与甲酰胺发生分子间N-还原N-杂环化反应，以中等的产率得到相应的喹唑啉衍生物。

We have been studying on ruthenium complex-catalyzed novel selective organic syntheses, especially from the view point of novel and selective carbon-carbon bond forming reactions. In the present work, ruthenium complex catalyzed novel methods for construction of carbon skeleton via pi-allylruthenium complexes as key intermediates or formyl C-H bond activation, together with the selective organic syntheses using related transition metal complex catalysts, have been developed. This year, 1. we have found that several eta^3-allylruthenium (II) complexes, such as (eta^3-allyl) Ru (OAc) (CO)_3 or cationic (eta^3-allyl) Ru (CO)_3] ^+ (OTf)^-, can function as both a nucleophile and an electrophile, i.e., as an ambiphile. 2. The following ruthenium complex-catalyzed novel transformations of alkyl formates were developed : selective decarbonylation of alkyl formates to alcohols, alkylation of arenes and alkenes using alkyl formates in neutral media, and addition of alcohols to alkenes. 3. Photo-, electro-, and thermal carbonylation of alkyl iodides in the presence of group 7 and 8-10 metal carbonyl catalysts, including ruthenium complexes. 4. In the course of the study on ruthenium complex-catalyzed reactions, we have found that Co_2 (CO)_8-catalyzed ring-opening carbonylation of oxiranes and oxetane smoothly proceeds with high regioselectivity under 1 atm of carbon monoxide at room temperature to give the corresponding beta- and gamma-siloxyamides in high yields, respectively. In addition, the PdCl_2 (PPh_3)_2-SnCl_2 system was found to show high catalytic activity for the reductive N-heterocyclization of nitrobenzenes to indole and 2H-indazole derivatives. The intermolecular reductive N-heterocyclization of 2-nitrobenzaldehyde or 2-nitrophenyl ketones with formamide using PdCl_2 (PPh_3)_2 with MoCl_5 was found to give the corresponding quinazoline derivatives in moderate yields.