Organometallic Chiral Hydrogen Bond Donor Catalysts for

Enantioselective Organic Reactions

Tathagata MUKHERJEE, John A. GLADYSZ*

Department of Chemistry, Texas A&M University, College Station, Texas, USA
E-mail: gladysz@mail.chem.tamu.edu

We have found that [Co(en)3]3+ and related Werner cations can be rendered soluble in organic
solvents using lipophilic anions such as "BArf".[1] Suitably functionalized derivatives act as
highly enantioselective catalysts for a variety of carbon-carbon bond forming reactions. The
mechanisms involve outer sphere activation of the electrophile by hydrogen bonding to the
NH moieties.

Figure 1. Organoruthenium systems.

In this presentation, these efforts will be extended to the organoruthenium system, Figure 1,
1+ X in which a cationic ruthenium fragment "preorganizes" a ligand with a variety of
hydrogen bond donor moieties. Either PF6 or BArf salts of 1+ or derivatives catalyze a
variety of carbon-carbon bond forming reactions, such as Friedel-Crafts alkylations of
indoles and additions of malonates to nitroalkenes. The polymerization of lactide to the
biodegradable polymer polylactide can also be catalyzed.[2] When enantiopure systems are
employed, ee values of >90% are routinely achieved for certain types of transformations,
Scheme 1.

Scheme 1. Enantioselective transformations catalyzed by

organometallic chiral hydrogen bond donors.

References
[1] Ganzmann, C.; Gladysz, J. A. Chem. Eur. J. 2008, 14, 5397.
[2] Thomas, C.; Gladysz, J. A. ACS Catalysis 2014, 5, 1134.