Development of Highly Efficient Asymmetric Reactions Based on Construction of Functionalized Multinucleating Chiral Reaction Field

开发一种实用、高效的手性分子构建方法对于探索新的药物和农用化学品至关重要。为了开发更有效的手性环境，多金属中心的加入应该更有效，因为金属的协同作用可以有效地控制反应物的立体化学过程，从而产生相应的光学活性化学物质。以酒石酸二异丙基（R，R）为手性助剂，催化具有二异丙基酰胺部分的硝基酮与g-取代烯丙醇的不对称1,3-偶极环加成反应，得到相应的3,4,5-三取代异恶唑烷，其对映选择性高达99%以上。以二异丙基（R，R）酒石酸酯为手性助剂，通过对映选择性高达96%的R-2-异恶唑啉，实现了由醛肟与次氯酸t-丁酯直接氧化原位生成的腈氧化物的不对称1,3-偶极环加成为2-丙烯-1-01。在CO和O2常压下，钯和铜盐催化n -甲酰基同丙烯胺反应可合成γ-内酰胺。用[PdCl_2(CH_3CN)_2]和CuCl进行单羰基化反应，得到3-甲基-2-吡咯烷酮，而用PdCl_2和CuCl_2将反应过程改为二羰基化反应，分别得到3-（烷氧羰基）甲基-2-吡咯烷酮，收率较高。在手性生物恶唑啉配体的存在下，可以得到具有光学活性的γ-内酰胺类化合物。

The development of a practical and efficient method for the construction of chiral molecules is essential to explore new medicines and agricultural chemicals. In order to develop more efficient chiral environment, incorporation of multi metal centers should be more effective, because the cooperative action of the metals can efficiently control the stereochemical course of the reactants to produce the corresponding optically active chemicals.A catalytic asymmetric 1,3-dipolar cycloaddition reaction of a nitrone possessing diisopropyl amide moiety to g-substituted allylic alcohols was achieved by using diisopropyl (R,R)-tartrate as a chiral auxiliary to afford the corresponding 3,4,5-trisubstituted isoxazolidines with excellent enantioselectivity up to over 99% ee.The asymmetric 1,3-dipolar cycloaddition of nitrile oxides, generated in situ from aldoximes by direct oxidation with t-butyl hypochlorite, to 2-propen-1-01 was achieved by utilizing diisopropyl (R,R)-tartrate as a chiral auxiliary to afford the corresponding R-2-isoxazolines with high enantioselectivity up to 96% ee.γ-Lactams can be synthesized from the reaction of N-tosyl homoallylamines catalyzed by palladium and copper salts under normal pressure of CO and O2 at rt. Monocarbonylation proceeded by the use of [PdCl_2(CH_3CN)_2] and CuCl to afford 3-methyl-2-pyrrolidinones, while the use of PdCl_2 and CuCl_2] chaneged the reaction course to the dicarbonylation to produce 3-(alkoxycarbonyl)methyl-2-pyrrolidinones in good yield, respectively. In the presence of chiral bioxazoline ligand, the optically active γ-lactams could be obtained.