通过多金属序列催化对α,β-不和碳基的远程功能化
Ciro Romano1, Daniele Fiorito1, Clément Mazet1
1Department of Organic Chemistry , University of Geneva , 30 quai Ernest Ansermet , 1211 Geneva , Switzerland.
Journal of the American Chemical Society
|October 8, 2019
概括
这项研究引入了新的多金属催化系统,用于远程功能化不和碳酸. 这些系统通过异构和玻利化等序列反应有效合成复杂分子.
科学领域:
- 有机化学
- 催化剂
- 合成方法
背景情况:
- 远程功能化α,β不和碳基仍然是一个合成挑战.
- 对于复杂的分子合成来说,开发有效的催化系统对序列转换至关重要.
研究的目的:
- 开发新的多金属序列催化系统,用于α,β不和碳酸的远程功能化.
- 实现非功能化并访问单一催化剂系统无法访问的复杂分子架构.
主要方法:
- 使用化 (Pd-H) 或化 (Ru-H) 异构化催化剂进行化.
- 序列催化,结合催化解化与铜催化β-玻里化.
- 使用[Pd/Cu]系统进行选性α-化和α-胺化.
- 通过使用[Pd/Os]或[Ru/Os]对进行同时功能化,将异构化与Sharpless非对称二化 (SAD) 进行整合.
主要成果:
- 通过使用多金属系统成功实现α,β不和碳酸的远程功能化.
- 作为关键中间体,产生热力学稳定的1,2-乙烯.
- 通过Pd/Cu联合催化获得一系列产品,包括β-玻里衍生物.
- 实现了高度反选择性的α-化和α-胺化.
- 通过异构化和SAD同时在基和同基位置进行功能失调.
- 通过异构化/二氧化/乳酸化序列合成具有高产率和选择性的自然存在的γ-丁.
结论:
- 多金属序列催化为α,β不和碳基的远程功能化提供了强大的策略.
- 开发的方法提供了有价值的合成中间体和复杂的分子结构.
- 催化系统在有机合成中表现出高效率,选择性和广泛适用性.
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