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核性添加与迁移性插入途径在黄金催化尾反应:一个计算研究
Peter H M Budzelaar1, Luca Rocchigiani2, Manfred Bochmann3
1Department of Chemistry, University of Naples Federico II, Via Cintia, Naples, I-80126, Italy.
Chemistry (Weinheim an der Bergstrasse, Germany)
|June 25, 2025
概括
计算研究表明,核友性攻击是黄金 (III) 催化Heck型反应中最受欢迎的途径. 基插入不太有利,即使是修改过的配体,1,2-插入比2,1-插入更受欢迎.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 计算化学计算化学
背景情况:
- 赫克反应是有机合成中的一个关键的碳-碳键形成反应.
- 黄金催化剂为Heck型反应提供了传统催化剂的替代品.
- 了解反应机制对于催化剂设计和优化至关重要.
研究的目的:
- 以计算方式研究P^N化Au(III) 催化Heck型化基形成中的初始反应步骤.
- 为了比较两个机械路径:基协调/插入和核友性攻击.
- 阐明连接体结构和固体阻碍对反应机制和区域选择性的影响.
主要方法:
- 用密度函数理论 (DFT) 的计算来建模反应路径.
- 探索了两个主要的机械替代方案:将烯插入金-碳键和对金 (III) 烯添加物的核友攻击.
- 分析了不同基质和配体替代剂 (P^N和P^P合物) 的作用.
主要成果:
- 发现核友性攻击途径在能量上比基插入更受青,因为P^N化Au(III) 复合体.
- 连接体转移影响显著控制反应通路,而固态效应显示最小的影响.
- 切换到P^P合物会破坏Au-Ph键的稳定,使基插入具有竞争力,优先选择1,2-插入区域化学.
结论:
- 该研究排除了基插入途径,以形成被研究的Au (III) 复合体催化的Heck型烯酸.
- 在研究条件下,核友性攻击是主要的机制.
- 催化剂设计,特别是联体选择 (P^N与P^P),可以影响不同机械路径的相对重要性.
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