Exploitation of New Catalytic Methods for the Construction of Carbon Frameworks and the Control of Reaction Fields

(1)直到本项目开始之前，还没有对高氧化态有机钌化学进行系统的研究。本项目首次成功地合成了几种新的含环戊二烯基（Cp）或五甲基环戊二烯基（Cp^*）配体的π-烯丙基钌（IV）配合物。对代表性的Cp^*Ru（pi-allyl）Br_2进行了X射线结构测定。详细研究了这些新的有机钌（IV）化合物中碳-钌（IV）键的化学反应性的几个重要方面。元素有机金属反应的合理组合提供了基于Ru（II）-Ru（IV）氧化还原通道的新型高选择性催化剂。丁二烯或1，3-戊二烯的线性齐聚反应用“CpRu^+”或“Cp^*Ru^+”型催化剂进行。此外，丁二烯或异戊二烯在温和条件下发生环状二聚反应，得到相应的具有极高相对分子质量的八元碳环骨架 ...更多信息 通过“Cp^*Ru^+”催化剂的立体和立体选择性。基于Cp^*RuX（diene）/AgOTf与共轭二烯之间的化学计量模型反应，阐明了合理的机理。(2)从Cu（I）或Ru（II）络合物的单电子转移被发现是分子内自由基加成形成C-C键的极其有效的氧化还原通道。这个最初的概念使化学计量的自由基环化反应成为均相催化过程。利用新的催化自由基环化反应从合适的无环前体如N-烯丙基三氯乙酰胺或烯丙基三氯乙酸酯衍生物开始构建三氯化γ-内酰胺或内酯骨架。这些新的方法被扩展到一些连续的多步自由基环化，并在内酰胺或内酯骨架上的偕碳原子的不对称诱导。(3)设计并成功合成了一种新型手性助剂双恶唑啉吡啶。它的铑（III）配合物为不对称催化提供了一个三齿的手性C_2反应场。少

(1) There have been no systematic study on organoruthenium chemistry with high oxidation states until this project was started. Several new pi-allyl ruthenium(IV) complexes bearing cyclopentadinyl(Cp) or pentamethylcyclopentadienyl(Cp^*) ligands were successfully prepared in this project for the first time. The X-ray structure determination of the representative Cp^*Ru(pi-allyl)Br_2 was undertaken. Several important aspects on the chemical reactivity of the carbon-ruthenium(IV) bonds in these new organoruthenium(IV) compounds were investigated in detail. Judicious combinations of the elemental organometallic reactions provide new highly selective catalyses based on Ru(II)-Ru(IV) redox channel. Linear oligomerization of butadiene or 1,3-pentadiene proceeds with "CpRu^+" or "Cp^*Ru^+" type catalysts. Furthermore, a cyclic dimerization of butadiene or isoprene was found to take place under mild condition to give the corresponding eight-membered carbocyclic frameworks with extremely high r … More egio- and stereo-selectivity by means of "Cp^*Ru^+" catalyst. A reasonable mechanism was elucidated based on a number of stoichiometric model reactions between Cp^*RuX(diene)/AgOTf and the conjugated dienes.(2) Single electron transfer from Cu(I) or Ru(II) complexes was found to be extremely effective redox channel to the intramolecular radical addition to form C-C bonds. This original concept makes stoichiometric radical cyclizations to homogeneous catalytic processes. New catalytic radical cyclization was exploited for the construction of trichlorinated gamma-lactam or lactone skeletons starting from the appropriate acyclic precursors such as N-allyltrichloroacetamide or allyltrichloroacetate derivatives. These new methodologies were extended to some sequential multi-step radical cyclization, and to the asymmetric induction at the geminal carbon atoms on the lactam or lactone skeletons.(3) Completely novel chiral auxiliary, bis(oxazolinyl)pyridine, was designed and successfully synthesized. Its rhodium(III) complex provides a terdentate meridional C_2-chiral reaction field for enantioselective catalysis. Less