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  

Application of Planar Chiral Cyclopentadienyl Rhodium Catalysts without Chiral Substituents in Asymmetric C—H Activation

作　　者：邹瑜 郭伟聪 汪君 Yu Zou;Weicong Guo;Jun Wang(School of Chemistry,Sun Yat-Sen University,Guangzhou 510006)

机构地区：[1]中山大学化学学院,广州510006

出　　处：《有机化学》2025年第2期466-476,共11页Chinese Journal of Organic Chemistry

基　　金：国家重点研发计划(No.2022YFA1504303);广东省高等学校功能分子工程基础研究卓越中心资助项目。

摘　　要：手性环戊二烯基铑(Cp Rh)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Cp Rh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.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.

关 键 词：环戊二烯基 铑 平面手性 不对称催化 碳氢键活化 

分 类 号：O643.3[理学—物理化学]