钯与铱催化烯丙基取代反应的对比教学

doi:10.12461/PKU.DXHX202512058

大学化学

所属专题：面向本科生教学的金属有机化学

钯与铱催化烯丙基取代反应的对比教学

张文文, 张培超, 许冰, 盖聪昊, 柴晓云, 赵庆杰, 邹燕

海军军医大学药学系有机化学教研室, 军事药学实验教学示范中心, 上海 200433

收稿日期:2025-12-18 录用日期:2026-03-04
通讯作者: 邹燕 E-mail:zouyan0622@126.com Yan Zou
基金资助:
2024年海军军医大学校级精品课程立项培育项目-有机化学II

A comparative pedagogy of Palladium- and Iridium-catalyzed allylic substitution

Wenwen Zhang, Peichao Zhang, Bing Xu, Conghao Gai, Xiaoyun Chai, Qingjie Zhao, Yan Zou

National Demonstration Center for Experimental Military Pharmacy Education, Department of Organic Chemistry, School of Pharmacy, Naval Medical University, Shanghai 200433, China

Received:2025-12-18 Accepted:2026-03-04
Contact: Yan Zou E-mail:zouyan0622@126.com

摘要/Abstract

摘要： 烯丙基取代反应是金属有机化学的典型反应类型之一。除钯外，铱、铜、钴、镍等金属亦能催化该类反应，且展现出各异的特性。然而，传统的本科教学多局限于钯催化体系，未能深入揭示过渡金属中心对反应调控的核心作用。为此，本文选取研究较为系统的钯与铱催化烯丙基取代反应作为对比教学案例，系统剖析二者在机理与区域选择性上的差异与互补，以阐述“催化剂结构决定反应性”的核心教学理念。

关键词: 金属有机化学, 钯催化, 铱催化, 烯丙基取代, 对比教学

Abstract: Transition-metal-catalyzed allylic substitution reactions are a fundamental topic in organometallic chemistry education. In addition to palladium, metals such as iridium, copper, cobalt, and nickel are also capable of catalyzing these reactions, each exhibiting distinct catalytic behaviors. However, traditional undergraduate courses often focus narrowly on palladium, failing to emphasize how the choice of transition metal critically directs reaction pathways and outcomes. To address this, we present a comparative study of Pd- and Ir-catalyzed allylic substitution as a pedagogical model. By systematically examining their mechanistic pathways along with regioselectivity profiles, we highlight how catalyst structure governs reactivity—a key conceptual thread in organometallic chemistry.

Key words: Organometallic chemistry, Palladium catalysis, Iridium catalysis, Allylic substitution, Comparative Pedagogy

张文文, 张培超, 许冰, 盖聪昊, 柴晓云, 赵庆杰, 邹燕. 钯与铱催化烯丙基取代反应的对比教学[J]. 大学化学, 2026, (): 2512058.

Wenwen Zhang, Peichao Zhang, Bing Xu, Conghao Gai, Xiaoyun Chai, Qingjie Zhao, Yan Zou. A comparative pedagogy of Palladium- and Iridium-catalyzed allylic substitution[J]. University Chemistry, 2026, (): 2512058.

链接本文: https://www.dxhx.pku.edu.cn/CN/10.12461/PKU.DXHX202512058

https://www.dxhx.pku.edu.cn/CN/Y2026/V/I/2512058

参考文献

[1] 麻生明. 金属参与的现代有机合成反应(修订版). 广州: 广东科技出版社, 2023.
[2] 宋礼成, 王佰全. 金属有机化学原理及应用. 北京: 高等教育出版社, 2012.
[3] R.H. Crabtree, 过渡金属有机化学(原著第5版). 江焕峰, 祝诗发, 主译. 北京: 科学出版社, 2012.
[4] 刘文博. 大学化学, 2026, in press. doi: 10.12461/PKU.DXHX202509131.
[5] 武少峰, 陈子仁, 夏昱, 张永红, 刘晨江. 化学教育, 2024, 45 (24), 16.
[6] 王帅, 许航线. 化学工程师, 2024, 38 (11), 78.
[7] J. Tsuji, H. Takahashi, M. Morikawa, Tetrahedron Lett. 1965, 6 (49), 4387.
[8] K.E. Atkins, W.E. Walker, R.M. Manyik, Tetrahedron Lett. 1970, 11 (43), 3821.
[9] T.P. Dang, H.B. Kagan, J. Chem. Soc. D 1971, 10, 481.
[10] B.M. Trost, T.J. Dietsch, J. Am. Chem. Soc. 1973, 95 (24), 8200.
[11] B.M. Trost, J. Am. Chem. Soc. 1977, 99 (5), 1649.
[12] R. Takeuchi, M. Kashio, Angew. Chem. Int. Ed. 1997, 36 (3), 263.
[13] J.P. Janssen, G. Helmchen, Tetrahedron Lett. 1997, 38 (46), 8025.
[14] B.M. Trost, M.L. Crawley, Chem. Rev. 2003, 103 (8), 2921.
[15] O. Pàmies, J. Margalef, S. Cañellas, J. James, E. Judge, P.J. Guiry, C. Moberg, J. B?ckvall, A. Pfaltz, M.A. Pericàs, et al., Chem. Rev. 2021, 121 (8), 4373.
[16] (a) T. Ohmura, J.F. Hartwig, J. Am. Chem. Soc. 2002, 124 (51), 15164. (b) S.T. Madrahimov, D. Markovic, J.F. Hartwig, J. Am. Chem. Soc. 2009, 131 (21), 7228.
[17] (a) W.-B. Liu, H. He, L.-X. Dai, S.-L. You, Synthesis 2009, (12) 2076. (b) W.-B. Liu, C. Zheng, C.-X. Zhuo, L.-X. Dai, S.-L. You, J. Am. Chem. Soc. 2012, 134 (10), 4812.
[18] J.Y. Hamilton, D. Sarlah, E.M. Carreira, Angew. Chem. Int. Ed. 2015, 54 (26), 7644.
[19] S.-L. You, X.-Z. Zhu, Y.-M. Luo, X.-L. Hou, L.-X. Dai, J. Am. Chem. Soc. 2001, 123 (30), 7471.
[20] R. Jiang, L. Ding, C. Zheng, S.-L. You, Science 2021, 371, 380.

钯与铱催化烯丙基取代反应的对比教学

A comparative pedagogy of Palladium- and Iridium-catalyzed allylic substitution

PDF

赞

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 5

Metrics

推荐阅读 0

[1]	张茜苑, 董锐, 杨洋, 丁佳鹏, 苗志伟. 钯催化4-乙烯基苯并噁嗪酮和茚-2-甲醛串联环化反应——介绍一个有机化学综合实验[J]. 大学化学, 2025, 40(9): 361 -367 .
[2]	胡诗雨, 武楷棂, 叶子豪, 刘永梅. 碳材料负载Pd催化甲酸盐分解制氢[J]. 大学化学, 2023, 38(8): 145 -155 .
[3]	罗一诚, 高延峰, 林维晟, 苗志伟. 钯催化串联环化反应合成2-苄基-3, 4-二羰基-6-苯基-9-乙烯基-2-氮杂螺[4.4]壬烷-7, 7-二羧酸乙酯——介绍一个有机化学综合实验[J]. 大学化学, 2023, 38(10): 250 -257 .
[4]	黄聪聪, 林莉莉, 李苏华, 张利, 苏成勇. 关于反馈键理论在小分子活化中的应用的讨论[J]. 大学化学, 2020, 35(7): 88 -94 .
[5]	王兰英, 王云侠, 李剑利. 以结构为主线结合对比法进行杂环化合物教学[J]. 大学化学, 2014, 29(5): 15 -19 .