利用机械化学进行烯烃促进的固态 C-N 交叉偶联反应。

Division of Applied Chemistry, Graduate School of Engineering, Hokkaido University, Sapporo, Hokkaido, 060-8628, Japan.

Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Sapporo, Hokkaido, 060-8628, Japan.

Nat Commun. 2019 Jan 10;10(1):111. doi: 10.1038/s41467-018-08017-9.

Palladium-catalyzed cross-coupling reactions are one of the most powerful and versatile methods to synthesize a wide range of complex functionalized molecules. However, the development of solid-state cross-coupling reactions remains extremely limited. Here, we report a rational strategy that provides a general entry to palladium-catalyzed Buchwald-Hartwig cross-coupling reactions in the solid state. The key finding of this study is that olefin additives can act as efficient molecular dispersants for the palladium-based catalyst in solid-state media to facilitate the challenging solid-state cross-coupling. Beyond the immediate utility of this protocol, our strategy could inspire the development of industrially attractive solvent-free palladium-catalyzed cross-coupling processes for other valuable synthetic targets.

钯催化交叉偶联反应是合成广泛的复杂功能化分子的最强大和通用的方法之一。然而，固态交叉偶联反应的发展仍然极其有限。在这里，我们报告了一种合理的策略，为钯催化的 Buchwald-Hartwig 交叉偶联反应在固态中提供了一种通用的途径。这项研究的关键发现是，烯烃添加剂可以作为钯基催化剂在固态介质中的有效分子分散剂，促进具有挑战性的固态交叉偶联。除了该协议的直接应用外，我们的策略还可以为其他有价值的合成目标激发开发具有工业吸引力的无溶剂钯催化交叉偶联过程。