Iron Catalysts for Selective Anti-Markovnikov Alkene Hydrosilylation Using Tertiary Silanes

Abstract

Alkene hydrosilylation, the addition of a silicon hydride (Si-H) across a carbon-carbon double bond, is one of the largest-scale industrial applications of homogeneous catalysis and is used in the commercial production of numerous consumer goods. For decades, precious metals, principally compounds of platinum and rhodium, have been used as catalysts for this reaction class. Despite their widespread application, limitations such as high and volatile catalyst costs and competing side reactions have persisted. Here, we report that well-characterized molecular iron coordination compounds promote the selective anti-Markovnikov addition of sterically hindered, tertiary silanes to alkenes under mild conditions. These Earth-abundant base-metal catalysts, coordinated by optimized bis(imino)pyridine ligands, show promise for industrial application.

Redox‐Active Ligands in Catalysis

“…The catalyst 10 also induces an internal olefin to chain walk to the terminal position prior to hydrosilylation. [19] Since 2000, bulky amidophenolate ligands (ap 2À ), popularized by the work of Wieghardt, have been widely exploited as redox-active ligands in which much of the electron trafficking occurs on the ligand rather than on the metal. [20] Soper and co-workers developed a [Co(ap) 2 ] À (11) system for Negishi-type CÀC cross-coupling reactions.…”

Iron‐Catalyzed, Atom‐Economical, Chemo‐ and Regioselective Alkene Hydroboration with Pinacolborane

“…Iron complexes of tridentate terpyridine and bis-(imino)pyridine ligands have been successfully applied to alkene hydrogenation [12] and hydrosilylation. [12,13] Encouragingly, the reactions using (terpy)FeCl 2 5 (5 mol %) and ( iPr PDI)FeCl 2 6 (5 mol %) afforded 2 a in 9 and 61 % yields, respectively (entries 5 and 6). The above data suggest that the use of a tridentate ligands is essential for iron-catalyzed alkene hydroboration.…”

Green synthesis of nitriles using non-noble metal oxides-based nanocatalysts

“…In the last decade, the development of non-noble metal-based catalysts [28][29][30][31] , especially nanomaterials [32][33][34] , for organic synthesis has become a prime topic and is crucial for the advancement of green and sustainable industrial processes. Last year, we reported the preparation of nanoscale cobalt and iron oxides, which constitute excellent catalysts for highly selective hydrogenation process 33,34 .…”