Toward a mild dehydroformylation using base-metal catalysis.
Toward a mild dehydroformylation using base-metal catalysis.
复制标题
DOI：
10.1039/c6sc04607j
复制
发表时间：
2017-03-01
期刊：
影响因子：
8.4
通讯作者：
Sorensen EJ
中科院分区：
文献类型：
--
作者：
Abrams DJ;West JG;Sorensen EJ
脱氢，一个具有挑战性的，探索不足的反应，可以在温和的条件下使用设计的合作贱金属催化剂系统进行。脱氢甲酰基化，即醛类产生烯烃、氢气和一氧化碳的反应，是一种强大的转化，尽管逆反应（氢甲酰基化）在工业上具有很高的重要性，但尚未开发。有趣的是，在温和的条件下，使用贱金属催化剂，大自然在胆固醇和相关甾醇的生物合成中通常会进行相关的转化，即氧化脱氢酶。相比之下，化学家最近开发了一种非氧化脱氢方法;然而，它需要高温和贵金属催化剂。对这两种方法的仔细研究为我们设计一种贱金属催化的温和脱氢方法提供了信息，该方法结合了每种方法的优点，同时避免了它们各自的缺点。重要的是，我们表明，合作贱金属催化提出了一个强大的，机械上独特的方法是很难实现使用传统的催化剂设计的反应。
Dehydroformylation, a challenging, underexplored reaction, can be performed under mild conditions using a designed cooperative base metal catalyst system. Dehydroformylation, or the reaction of aldehydes to produce alkenes, hydrogen gas, and carbon monoxide, is a powerful transformation that is underdeveloped despite the high industrial importance of the reverse reaction, hydroformylation. Interestingly, nature routinely performs a related transformation, oxidative dehydroformylation, in the biosynthesis of cholesterol and related sterols under mild conditions using base-metal catalysts. In contrast, chemists have recently developed a non-oxidative dehydroformylation method; however, it requires high temperatures and a precious-metal catalyst. Careful study of both approaches has informed our efforts to design a base-metal catalyzed, mild dehydroformylation method that incorporates benefits from each while avoiding several of their respective disadvantages. Importantly, we show that cooperative base metal catalysis presents a powerful, mechanistically unique approach to reactions which are difficult to achieve using conventional catalyst design.