混合酸 η5-CpRuCl(PR3) 2复合物作为终端基因的抗马尔科夫尼科夫水解的双功能催化剂
Florian Boeck1, Thomas Kribber, Li Xiao
1Department Chemie, Technische Universität München, Lichtenbergstrasse 4, 85748 Garching bei München, Germany.
这项研究表明,催化剂对于抗马尔科夫尼科夫基因化成化物的有效性保持不变,即使经过配体修饰. 修改后的催化剂在富含水的环境中有效地将基因转化为化物.
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:
- 复合物是各种有机转变的有效催化剂.
- 基因的抗马尔科夫尼科夫水合是一种有价值的合成途径,可以生成化物.
- 连接物修饰可以调整金属催化剂的活性和选择性.
研究的目的:
- 为了研究一种改性复合物的催化活性,用于终端基因的抗马尔科夫尼科夫水化.
- 探索从前体复合体中在现场生成活性催化物种.
- 为了优化反应条件,从基中有效合成化物.
主要方法:
- 合成和表征-Cp复合体与素配体.
- 通过平衡前体复合物,在现场生成活性催化剂.
- 优化反应参数,包括温度,溶剂成分和催化剂负载.
- 使用在位生成的催化剂,对终端基因的制剂抗马尔科夫尼科夫水化.
主要成果:
- 对于抗马尔科夫尼科夫基因水解的[CpRu(L) ((2) ((MeCN) ]PF(6) 的催化活性在将一个连接体 (L) 替换为三 (PPh ((3)) 时保持不变.
- 在乙中,CpRuCl ((PPh ((3)) ((2),CpRuCl ((L)) ((PPh ((3)) 和CpRuCl ((L)) ((2) 的平衡混合物作为一种高度活跃的现场催化剂.
- 在富含水 (4:1乙/水) 的介质中,在3-18小时内在60°C时达到2mol%Ru的终端基因转化为基的有效转化.
- 在160°C时,反应显著加速,在不到15分钟内完成.
结论:
- 修改后的催化剂系统对终端基因到化物的反马尔科夫尼科夫水合非常有效.
- 在现场催化剂生成为准备合成提供了一种多功能和活跃的催化系统.
- 开发的方法在温和或加速条件下提供了一种高效且潜在可扩展的化物途径.
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