McArthur Gillian, Docherty Jamie H, Hareram Mishra Deepak, Simonetti Marco, Vitorica-Yrezabal Iñigo J, Douglas James J, Larrosa Igor
Department of Chemistry, University of Manchester, Manchester, UK.
Department of Chemistry, Lancaster University, Lancaster, UK.
Nat Chem. 2024 Jul;16(7):1141-1150. doi: 10.1038/s41557-024-01481-5. Epub 2024 Apr 3.
Versatile, efficient and robust (pre)catalysts are pivotal in accelerating the discovery and optimization of chemical reactions, shaping diverse synthetic fields such as cross-coupling, C-H functionalization and polymer chemistry. Yet, their scarcity in certain domains has hindered the advancement and adoption of new applications. Here we present a highly reactive air- and moisture-stable ruthenium precatalyst (BuCN)Ru(HO), featuring a key exchangeable water ligand. This versatile precatalyst drives an array of transformations, including late-stage C(sp)-H arylation, primary/secondary alkylation, methylation, hydrogen/deuterium exchange, C(sp)-H oxidation, alkene isomerization and oxidative cleavage, consistently outperforming conventionally used ruthenium (pre)catalysts. The generality and applicability of this precatalyst is exemplified through the potential for rapid screening and optimization of photocatalytic reactions with a suite of in situ generated ruthenium photocatalysts containing hitherto unknown complexes, and through the rapid discovery of reactivities previously unreported for ruthenium. The diverse applicability observed is suggestive of a generic platform for reaction simplification and accelerated synthetic discovery that will enable broader applicability and accessibility to state-of-the-art ruthenium catalysis.
多功能、高效且稳健的（预）催化剂对于加速化学反应的发现和优化至关重要，塑造了诸如交叉偶联、C-H官能化和聚合物化学等各种合成领域。然而，它们在某些领域的稀缺性阻碍了新应用的发展和采用。在此，我们展示了一种高反应性的空气和水分稳定的钌预催化剂(BuCN)Ru(HO)，其具有关键的可交换水配体。这种多功能预催化剂驱动了一系列转化反应，包括后期C(sp)-H芳基化、一级/二级烷基化、甲基化、氢/氘交换、C(sp)-H氧化、烯烃异构化和氧化裂解，始终优于传统使用的钌（预）催化剂。通过对一系列原位生成的含有迄今未知配合物的钌光催化剂进行光催化反应的快速筛选和优化潜力，以及通过快速发现钌以前未报道的反应活性，例证了这种预催化剂的通用性和适用性。观察到的多样适用性暗示了一个用于简化反应和加速合成发现的通用平台，这将使最先进的钌催化具有更广泛的适用性和可及性。
