Jankins Tanner C, Blank Philip M, Brugnetti Andrea, Boehm Philip, Aouane Françoise A, Morandi Bill
Laboratorium für Organische Chemie, ETH Zürich, 8093, Zürich, Switzerland.
Nat Commun. 2024 Oct 30;15(1):9397. doi: 10.1038/s41467-024-53281-7.
Hydrogen atom transfer (HAT) from a metal-hydride is a reliable and powerful method for functionalizing unsaturated C-C bonds in organic synthesis. Cobalt hydrides (Co-H) have garnered significant attention in this field, where the weak Co-H bonds are most commonly generated in a catalytic fashion through a mixture of stoichiometric amounts of peroxide oxidant and silane reductant. Here we show that the reverse process of HAT to an alkene, i.e. hydrogen atom abstraction of a C-H adjacent to a radical, can be leveraged to generate catalytically active Co-H species in an application of shuttle catalysis coined shuttle HAT. This method obviates the need for stoichiometric reductant/oxidant mixtures thereby greatly simplifying the generation of Co-H. To demonstrate the generality of this shuttle HAT platform, five different reaction manifolds are shown, and the reaction can easily be scaled up to 100 mmol.
在有机合成中，从金属氢化物进行氢原子转移（HAT）是使不饱和碳 - 碳键官能化的一种可靠且强大的方法。钴氢化物（Co - H）在该领域已备受关注，其中弱Co - H键最常见的是以化学计量的过氧化物氧化剂和硅烷还原剂的混合物通过催化方式生成。在此，我们表明，在一种称为穿梭HAT的穿梭催化应用中，HAT到烯烃的逆过程，即从与自由基相邻的C - H上夺取氢原子，可用于生成具有催化活性的Co - H物种。该方法无需化学计量的还原剂/氧化剂混合物，从而极大地简化了Co - H的生成。为了证明该穿梭HAT平台的通用性，展示了五种不同的反应体系，并且该反应可以轻松放大至100 mmol。
