在赫克反应中的区域化学的电子控制
Henrik von Schenck1, Björn Akermark, Mats Svensson
1Materials Physics, Royal Institute of Technology, SE-164 40 Kista, Sweden. schenck@imit.kth.se
Journal of the American Chemical Society
|March 20, 2003
概括
中性 ((II) 复合物有利于 2,1-插入烯,与阴离子复合物不同. 立体和电子因素可以调整,以控制Heck反应中的区域选择性.
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.
- 计算化学的计算化学
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.
- (II) 复合物是赫克反应中广泛使用的催化剂.
- 控制迁徙插入的区域选择性是优化催化结果的关键.
研究的目的:
- 通过使用中性结合剂连接物,研究的迁移性插入到 ((II) - 键中.
- 了解影响区域选择性的电子和固态因素 (1,2-vs. 2,1-插入).
- 探索控制催化赫克反应中的区域化学的方法.
主要方法:
- 使用密度函数理论 (DFT) 的计算.
- 对含有N-N,P-O和N-O合联体的中性 ((II) 复合物的分析.
- 研究过渡状态能量和固态相互作用.
主要成果:
- 中性 ((II) 复合物表现出对 2,1-插入的偏好.
- 变态影响在不对称的连接体系统中显著影响插入屏障.
- 发现,固体效应通过破坏2,1过渡状态来增强1,2-选择性.
结论:
- 在Pd-键中插入烯的区域选择性是可控制的.
- 连接体的电子和固态调节的组合允许精确控制赫克反应的区域化学.
- 这项研究为设计更有选择性的催化剂提供了洞察力.
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