EaStCHEM School of Chemistry, University of Edinburgh, Joseph Black Building, David Brewster Road, Edinburgh EH9 3FJ, UK.
GSK Medicines Research Centre, Gunnels Wood Road, Stevenage, Hertfordshire SG1 2NY, UK.
Nat Chem. 2017 Jan 9;9(6):595-600. doi: 10.1038/nchem.2697.
First-row, earth-abundant metals offer an inexpensive and sustainable alternative to precious-metal catalysts. As such, iron and cobalt catalysts have garnered interest as replacements for alkene and alkyne hydrofunctionalization reactions. However, these have required the use of air- and moisture-sensitive catalysts and reagents, limiting both adoption by the non-expert as well as applicability, particularly in industrial settings. Here, we report a simple method for the use of earth-abundant metal catalysts by general activation with sodium tert-butoxide. Using only robust air- and moisture-stable reagents and pre-catalysts, both known and, significantly, novel catalytic activities have been successfully achieved, covering hydrosilylation, hydroboration, hydrovinylation, hydrogenation and [2π+2π] alkene cycloaddition. This activation method allows for the easy use of earth-abundant metals, including iron, cobalt, nickel and manganese, and represents a generic platform for the discovery and application of non-precious metal catalysis.
首行,丰富的地球金属为替代贵金属催化剂提供了一种廉价且可持续的选择。因此,铁和钴催化剂作为烯烃和炔烃氢官能化反应的替代品引起了人们的兴趣。然而,这些反应需要使用对空气和水分敏感的催化剂和试剂,这不仅限制了非专业人士的采用,也限制了其适用性,特别是在工业环境中。在这里,我们报告了一种使用丰富的地球金属催化剂的简单方法,即用叔丁醇钠进行一般活化。仅使用坚固的对空气和水分稳定的试剂和预催化剂,已经成功地实现了已知的和显著的新催化活性,涵盖了硅氢化、硼氢化、氢甲酰化、氢化和[2π+2π]烯烃环加成。这种活化方法允许容易地使用丰富的地球金属,包括铁、钴、镍和锰,并代表了发现和应用非贵金属催化的通用平台。