Pradeep Cheruku

Iridium-N,P-Ligand-Catalyzed Enantioselective Hydrogenation of Diphenylvinylphosphine Oxides and Vinylphosphonates

Diphenylvinylphosphine oxides and di- and trisubstituted vinylphosphonates have been employed as substrates in iridium-catalyzed asymmetric hydrogenations. Complete conversions and excellent enantioselectivities (up to and above 99% ee) were observed for a range of substrates with both aromatic and aliphatic groups at the prochiral carbon. We have also hydrogenated electron-deficient carboxyethylvinylphosphonates with excellent stereoselectivity (up to and above 99% ee). The hydrogenated products of both classes of substrates are synthetically useful intermediates.

Iridium-catalyzed enantioselective hydrogenation of vinyl boronates

The first Ir-catalyzed asymmetric hydrogenations of vinyl boronates have been performed using low catalyst loadings (0.5 mol%) and pressure (as low as 1 bar). Good selectivities (76-98% ee) were obtained for a range of substrates.

Asymmetric Hydrogenation of Di and Trisubstituted Enol Phosphinates with N,P-Ligated Iridium Complexes

The iridium-catalyzed asymmetric hydrogenation of various di- and trisubstituted enol phosphinates has been studied. Excellent enantioselectivities (up to >99% ee) and full conversion were observed for a range of substrates with both aromatic and aliphatic side chains. Enol phosphinates are structural analogues of enol acetates, and the hydrogenated alkyl phosphinate products can easily be transformed into the corresponding alcohols with conservation of stereochemistry. We have also hydrogenated, in excellent ee, several purely alkyl-substituted enol phosphinates, producing chiral alcohols that are difficult to obtain highly enantioselectively from ketone hydrogenations.

Phosphine-Free Cp*Ru(Diamine) Catalysts in the Hydrogenation of Imines

We previously reported the phosphine-free Cp*Ru(diamine)-catalyzed hydrogenation of aryl methyl ketones. Herein we present the first report of ruthenium-diamine-catalyzed imine hydrogenation to form amines. The most effective catalyst, I/KOtBu, completely converted several imines to amines at room temperature. The effect of electron-donating and -withdrawing groups on the reaction was investigated using a suitable series of substrates. The asymmetric version of the reaction was studied for two substrates, and the chiral amine products could be obtained in moderate enantiomeric excess.