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New cooperative multifunctional catalysts derived from Cinchona Alkaloids

Final Activity Report Summary - COMULTICAT (New Cooperative Multifunctional Catalysts Derived from Cinchona Alkaloids)

Combinations of organocatalysts and transition metal catalysts can give rise to new reactivities in a wide range of reactions and in certain circumstances maintain the high levels of enantiocontrol.

In the first part of the fellowship, a one-pot, multistep reaction cascade to cyclopentenes from alpha, beta-unsaturated ketones and propargylated carbon acids through a combination of organocatalysis and transition metal ion catalysis was developed. Initiated by an amine catalysed Michael addition of propargylated pro-nucleophiles to alpha, beta-unsaturated ketones, the enamine intermediate undergoes an intramolecular attack onto the tethered, copper (I) activated, alkynyl group. Subsequent, protonolysis, hydrolysis and isomerisation steps affords the cyclopentene products in good to excellent yields. The reaction cascade was simple to perform, occurs under mild condions and is broad in scope.

In the second part of the fellowship, a mutually compatible and cooperative combination of copper (I) triflate and bifunctional 9-amino (9-deoxy) epicinchona-derived urea compounds for the enantioselective Conia-ene cyclization of alkyne tethered b-ketoester substrates was developed. Demonstrating a powerful concept of combining, in situ, catalytically inactive pre-catalyst ligands with catalytically inactive transition metal ion complexes to reversibly create a catalytically active combination of the two, the reaction was efficient, broad in scope, easy to perform and allows access to chiral cyclopentane products with high enantiocontrol.