不含手性取代基的平面手性环戊二烯基铑催化剂在不对称碳氢键活化中的应用

doi:10.6023/cjoc202410002

摘要/Abstract

手性环戊二烯基铑(CpRh)催化剂由于具有高稳定性、可调节性和独特的反应性而被广泛应用于不对称碳氢键活化反应中, 可以将简单有机分子高效转化为具有中心手性、平面手性、轴手性和螺旋手性的分子. 根据手性CpRh催化剂中Cp配体是否具有手性, 可将催化剂分为手性Cp衍生的催化剂和前手性Cp衍生的催化剂. 目前, 前者的开发已取得巨大成功, 而后者的研究较少. 综述了不含手性取代基的平面手性环戊二烯基铑催化剂的合成及其在不对称碳氢键活化反应中的应用, 并介绍了反应机理及立体控制模型. 最后, 探讨了该领域所面临的机遇与挑战.

关键词: 环戊二烯基, 铑, 平面手性, 不对称催化, 碳氢键活化

Owing to the high stability, adjustability, and unique reactivity of chiral cyclopentadienyl rhodium (CpRh) catalysts, they are widely used in asymmetric C—H activation reactions for rapid construction of diverse and complex molecules bearing central chirality, planar chirality, axial chirality and helical chirality. According to whether the Cp ligand in chiral CpRh catalysts is chiral, the catalysts can be divided into chiral Cp-derived catalysts and prochiral Cp-derived catalysts. Currently, the development of the former has achieved great success, while research on the latter is relatively limited. The syntheses of planar chiral cyclopentadienyl rhodium catalysts without chiral substituents and their application in asymmetric C—H activation are summarized. The stereocontrol model and the mechanism are also discussed. Finally, the opportunities and challenges in developing the planar chiral cyclopentadienyl rhodium catalysts without chiral substituents are discussed.

Key words: cyclopentadienyl, rhodium, planar chirality, asymmetric catalysis, C—H activation

引用此文

邹瑜, 郭伟聪, 汪君. 不含手性取代基的平面手性环戊二烯基铑催化剂在不对称碳氢键活化中的应用[J]. 有机化学, 2025, 45(2): 466-476.

Yu Zou, Weicong Guo, Jun Wang. Application of Planar Chiral Cyclopentadienyl Rhodium Catalysts without Chiral Substituents in Asymmetric C—H Activation[J]. Chinese Journal of Organic Chemistry, 2025, 45(2): 466-476.

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图/表 11

图1. 手性CpRh催化剂中的两类Cp

Figure 1. Two types of Cp ligands for chiral CpRh catalysts

图式1. 平面手性CpRh催化剂5和8的合成

Scheme 1. Synthesis of planar chiral CpRh catalyst 5 and 8

图式2. (Rp)-5在不对称[4＋2]环化反应中的应用及催化反应立体控制模型

Scheme 2. Application of (Rp)-5 in asymmetric [4＋2] annulation and stereocontrol model for the reaction

图式3. 平面手性CpRh催化剂(Rp)-13和(Sp)-13的合成及其在不对称碳氢键活化反应中的应用

Scheme 3. Synthesis of planar chiral CpRh catalyst (Rp)-13 and (Sp)-13 and their application in asymmetric [4＋2] annulation

图式4. 平面手性CpRh催化剂23的合成

Scheme 4. Synthesis of planar chiral CpRh catalyst 23

图式5. (Sp)-23a在不对称合成C—N轴手性N-芳基吲哚酮中的应用及催化反应立体控制模型

Scheme 5. Synthesis of C—N axially chiral N-aryloxindoles using (Sp)-23a and stereocontrol model for the reaction

图式6. (Sp)-23e在不对称[4＋2]环化反应中的应用及催化反应立体控制模型

Scheme 6. Application of (Sp)-23e in asymmetric [4＋2] annulation and stereocontrol model for the reaction

图式7. 前手性Cp配体的设计和合成及平面手性CpRh的手性二烯拆分策略

Scheme 7. Design and synthesis of prochiral Cp ligands and chiral resolution of planar chiral CpRh complexes by chiral diene

图式8. 36b催化合成手性氢化菲啶酮及反应立体控制模型

Scheme 8. Synthesis of chiral hydrophenanthridinone catalyzed by 36b and stereocontrol model for the reaction

图式9. 36d催化合成手性二氢异喹诺酮

Scheme 9. Synthesis of chiral dihydroisoquinolinones catalyzed by 36d

图式10. 平面手性茚铑催化剂45的合成及其在不对称碳氢键活化反应中的应用与立体控制模型

Scheme 10. Synthesis of planar chiral indenyl rhodium catalyst 45, its application in enantioselective allylic C—H amidation and stereocontrol model for the reaction

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