选择性转移半化由铁PCP子基复合物催化的基
Heiko Schratzberger1, Berthold Stöger2, Luis F Veiros3
1Institute of Applied Synthetic Chemistry, TU Wien, Getreidemarkt 9/163-AC, A-1060 Wien, Austria.
新的铁复合物催化了基化,选择性地形成Z-基. 在温和条件下,n-propyl复合物显示出比甲基复合物更高的活性.
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.
- 有机合成 有机合成
背景情况:
- 铁复合物越来越多地被研究为可持续的催化剂.
- 基迁移到碳联体是许多催化循环中的关键步骤.
- 转移化为减少不和化合物提供了一种实用的方法.
研究的目的:
- 为了合成和表征新的铁 (II) 基复合物.
- 为了研究它们在基因转移化中的催化活性.
- 阐明反应机制和影响催化性能的因素.
主要方法:
- 通过铁的中间体合成铁 (II) 基复合物.
- 终端和内部基因的催化转移化,使用基和异醇作为源.
- 机械研究涉及乳标记和DFT计算.
主要成果:
- 成功合成了两种稳定铁 (II) 基复合物[Fe (κ3PCP-PCP-iPr) (CO) 2 (R) ] (R=n-propyl,methyl) ],这些复合物具有非常高的稳定性.
- 这两种复合物都有效地催化了在室温下与低催化剂负荷 (0.5mol%) 的基因的转移化.
- 复合物表现出比甲基复合物更高的催化活性,与更快的基迁移动力学相一致.
- 这些反应仅从内部基中产生Z-基,没有过度化,并且耐受各种功能组.
结论:
- 合成的铁 (II) 基复合物是基转移化过程中有效的前催化剂.
- 基联体结构显著影响催化活性,n-propyl比甲基更有效.
- 开发的催化系统具有高度选择性,对功能组具有耐受性,在温和条件下运行,提供了有价值的合成工具.
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