The enantioselective hydrogenation of olefins is one of the most powerful transformations for preparing optically active compounds because of its atom economy and operational simplicity. Whereas the reduction of olefins containing an adjacent polar group by Rh- and Ru- catalysts modified with phosphorus ligands has been successfully achieved, the hydrogenation of minimally functionalized olefins is less developed. Iridium complexes with chiral P-N ligands have become established as one of the most efficient catalyst types for this reaction. We recently found that the introduction of a phosphite moiety in P,N-ligands is highly advantageous, because they show greater substrate versatility than previously used phosphine or phosphinite counterparts.Herein a modular set of heterodonor based P-thioether ligands has been applied to the title reaction. Excellent ligands have been identified for a range of substrates, including tri- and disubstituted substrates containing a neighboring polar group, where we now have reached enantioselectivities of 99% for a range of substrates.

Development of new P-S ligands for the highly enantioselective hydrogenation of minimally functionalized olefins

245th National Meeting (2013)

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