Takemoto1 developed bifunctional thiourea 1  which is able to activate electrophiles (through hydrogen bonds) and nucleophiles (by deprotonation) at the same time. The 3,5-bistrifluoromethylphenyl used in thioureas and boronate ureas 2  provide good hydrogen bonding with substrates. Nevertheless, Berkessel2 has shown that even though the catalytic activity is good, introducing chiral substituents improves selectivity 3-4 . Ellman and Jacobsen have used chiral sulfinamides at the nitrogen to have a chiral substituent with good hydrogen bond donor properties 5 . Having this background, we envisioned bifunctional thioureas 6  that incorporate chiral amines with a-trifluoromethyl group increase the capacity to donate hydrogen bonds3 and are able to modulate the catalyst chiral environment. We had proved these organocatalysts in the Michael addition of 1,3-dicarbonyl compounds to �-nitrostyrene and the dynamic kinetic resolution of azlactones. It was found that a strong match-mismatch relationship with diastereomeric catalysts and up to 92% ee in Michael addition and 80 % ee for the phenylalanine azlactone opening. (1)   Okino, T.; Hoashi, Y.; Takemoto, Y. J. Am. Chem. Soc. 2003 , 125, 12672.(2)   Berkessel, A.; Mukherjee, S.; Thomas, N. M.; Cleemann, F.; Roland, K.; Brandenburg, M.; Neud�rfl, J.-M.; Lex, J. Org. Biomol. Chem. 2006 , 4, 4319.(3)   Trejo-Huizar, K. E.; Ortiz-Rico, R.; Pe�a-Gonz�lez, M. A.; Hern�ndez-Rodr�guez, M. New. J. Chem. 2013 , 37, 2610.

Application of bifunctional organocatalysts containing chiral amines with a-trifluoromethyl group

248th National Meeting (2014)

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