不对称催化已成为现代有机合成领域中手性分子高效构建的关键核心技术之一。该方法能够高效地调控反应产物的对映选择性，为合成手性药物、天然产物以及功能型光学材料提供具有价值的合成策略。5-氨基吡唑结构单元不仅在有机合成领域中扮演着关键角色，还在药理学研究中展现出了潜在的应用价值。同时，5-氨基吡唑是多种抗炎药、抗肿瘤制剂等药物的关键骨架结构。本文主要包括以下两部分研究工作：

1.采用手性Ni（II）/联吡啶N,O配体催化体系，我们实现了5-氨基吡唑与3-烯基氧化吲哚的不对称Friedel-Crafts酰基化反应。为得到最佳的反应条件，本课题对金属镍、手性配体、溶剂和温度以及配体和金属的用量进行一系列考察后，确定了反应的最优条件：即10 mol%的Ni(OTf)₂作为金属催化剂，11 mol%的L12作为手性配体，DCM作为溶剂，在室温下进行反应。在最佳条件下，我们以89-98%的产率和56-99% ee的对映选择性合成了36种手性螺环氧化吲哚化合物。此外，通过克级放大实验和衍生化实验，证实了该方法的实用性。

2.手性磷酸作为催化剂实现了5-氨基吡唑和偶氮萘衍生物的不对称芳基化反应。本课题对催化剂的类型、溶剂的种类、反应的温度和催化剂的用量进行一系列考察后，确定了反应的最优条件：即15 mol%的C3作为催化剂，DCM作为溶剂，在0 ℃下进行反应。在最优条件下，我们以73-89%的产率和75-95% ee的对映选择性合成了30种轴手性芳基吡唑化合物。此外，通过克级放大实验和衍生化实验，验证了该策略的应用价值。

Asymmetric catalysis is a key for the efficient construction of chiral molecules in the field of modern organic synthesis. This method enables precise control over the production enantioselectivity, offering a valuable synthetic strategy for chiral molecules, including chiral drugs, natural products, and functional optical materials. The 5-aminopyrazole scaffold is not only a key structural motif in organic synthesis but also exhibits promising potential in drug discovery. Notably, this core framework constitutes the essential skeleton of numerous therapeutic agents, including anti-inflammatory drugs and antitumor medications. This paper presents the following two research components:

Asymmetric Friedel-Crafts acylation of 5-aminopyrazoles with 3-alkenyloxindoles was achieved using chiral Ni(II)/bipyridine N, O ligand-catalyzed system. In order to identify the optimal reaction conditions, we systematically screened nickel sources, chiral ligands, solvents, temperatures, and metal-to-ligand ratios. The optimized conditions were determined as follows: 10 mol% Ni(OTf)₂ as the metal catalyst, 11 mol% L12 as the chiral ligand in dichloromethane (DCM) at room temperature. The optimized protocol afforded 36 structurally diverse spirooxindoles in excellent yields (89-98%) with good to outstanding enantiocontrol (56-99% ee). The synthetic utility was highlighted by successful gram-scale implementation and downstream functionalization.

A chiral phosphoric acid-catalyzed asymmetric arylation of 5-aminopyrazoles with naphthyl azodicarboxylates has been developed. Through systematic optimization of catalyst structures, solvent systems, reaction temperatures, and catalyst loadings, the optimal conditions were identified as: 15 mol% CPA C3 in dichloromethane (DCM) at 0°C. Under these conditions, a series of 30 axially chiral arylpyrazole derivatives were obtained in good to excellent yields (73-89%) with high enantioselectivity (75-95% ee). The synthetic utility of this methodology was further validated by gram-scale synthesis and subsequent derivatization experiments.

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