Readily Accessible Bulky Iron Catalysts exhibiting Site Selectivity in the Oxidation of Steroidal Substrates

Bulky iron complexes are described that catalyze the site‐selective oxidation of alkyl C−H bonds with hydrogen peroxide under mild conditions. Steric bulk at the iron center is introduced by appending trialkylsilyl groups at the meta‐position of the pyridines in tetradentate aminopyridine ligands, and this effect translates into high product yields, an enhanced preferential oxidation of secondary over tertiary C−H bonds, and the ability to perform site‐selective oxidation of methylenic sites in terpenoid and steroidal substrates. Unprecedented site selective oxidation at C6 and C12 methylenic sites in steroidal substrates is shown to be governed by the chirality of the catalysts. Eisen oxidiert: Eisenkomplexe mit sperrigen Silylsubstituenten katalysieren die regioselektive Oxidation von Alkyl‐C‐H‐Bindungen mit Wasserstoffperoxid unter milden Bedingungen. Zum Beispiel wird gezeigt, dass die ungewöhnliche regioselektive Oxidation der C6‐ und C12‐Methylenzentren in steroidalen Substraten von der Chiralität des Katalysators bestimmt wird.