Ruthenium Complex-Catalyzed Highly Selective Organic Syntheses

我们一直在研究钌配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-碳成键反应的角度进行研究。本文发展了以钌配合物为关键中间体或甲酰基C-H键活化钌配合物构建碳骨架的新方法，以及利用相关过渡金属配合物催化剂进行选择性有机合成的新方法。今年，1。我们发现一些eta^3-烯丙基钌（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，即作为两亲试剂。2. 本文研究了钌络合物催化甲酸烷基酯的几种新转化：甲酸烷基酯选择性脱羰制醇、甲酸烷基酯在中性介质中催化芳烃和烯烃烷基化、烯烃加成醇。3. 在7族和8-10族金属羰基催化剂（包括钌配合物）存在下的碘化烷基的光、电和热羰基化反应。4. 在钌配合物催化反应的研究过程中，我们发现Co_2 (CO)_8催化的氧烷和氧烷开环羰基化反应在室温1atm的一氧化碳条件下以高的区域选择性顺利进行，分别高产出相应的-和-硅氧酰胺。此外，PdCl_2 (PPh_3)_2-SnCl_2体系对硝基苯n -杂环还原制吲哚和2h -吲哚衍生物具有较高的催化活性。用PdCl_2 (PPh_3)_2和MoCl_5与甲酰胺进行2-硝基苯甲醛或2-硝基苯酮的分子间n -杂环化反应，得到了相应的产率中等的喹唑啉衍生物。

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.