A Predictably Selective Palladium-Catalyzed Aliphatic C–H Oxygenation

Abstract

Direct oxygenation of nonactivated aliphatic C-(sp 3 )−H groups with peroxycarboxylic acids in the presence of palladium tris(pyridylmethyl)amine complex (0.6 mol %) is reported, providing the corresponding hydroxylated derivatives in up to 94% yields. The oxidation of 3°C−H groups occurs stereospecifically, with the catalyst system demonstrating extremely high sensitivity to electronic effects (adamantane oxidation: 3°:2°u p to >300). This suggests potential applications for the 3°regioselective oxidative functionalization of complex molecules of natural origin.

Practical and Scalable Synthesis of 1,3-Adamantanediol

“…The synthesis of 1,3-adamantanediol from adamantane usually requires the addition of metal catalysts, for example, cobalt, − palladium, vanadium, , ruthenium, − titanium, , manganese, nickel, and molybdenum. , Although the reaction can be carried out under milder conditions, isolation yields and selectivity are usually poor (40%<). − Table S3 lists the reaction conditions and yields in the literature. In addition, Xu and co-workers obtained a higher isolation yield (71%), but a large amount of sodium acetate solution was formed.…”

“…The synthesis of 1,3-adamantanediol from adamantane usually requires the addition of metal catalysts, for example, cobalt, 42−45 palladium, 46 vanadium, 47,48 ruthenium, 49−55 titanium, 56,57 manganese, 58 nickel, 59 and molybdenum. 60,61 Although the reaction can be carried out under milder conditions, isolation yields and selectivity are usually poor (40%<).…”