Asymmetricβ- Lactams 10mo% benzoyl quinine (NR3") NR3 NMe2 NMe R R3N Ts N 45-65% yield NR3*+ H CO2Et 99/1 cis/trans Eto h2C R 96-99%ee R=alkyl, aryl, alkoxy Taggi, A E; Hafez, A M. Wack, H. Young, B. Drury, W.J. Ill, Leckta, T J.Am.chem.Soc.2000.122.7831
Asymmetric b-Lactams O Cl R NMe2 NMe2 N Ts H CO2 Et N Ts O EtO2 H2 C R O R H 45 - 65% yield 99/1 cis/trans 96 - 99% ee R = alkyl, aryl, alkoxy 10 mol% benzoyl quinine (NR3*) NR3* O *R3N R NR3* + Taggi, A.E.; Hafez, A. M.; Wack, H.; Young, B.; Drury, W. J. III, Leckta, T. J. Am. Chem. Soc. 2000, 122, 7831
Asymmetric Baylis-Hillman OHo CF CF 10mo% O′CF3DMF,-5 O CF O2N 1 h O2N A一74%ye (R)-10%ee OH 58% yield (R)-91%ee High enantioselectivities(91-99%ee) Modest yields(31-58%) Iwabuchi, Y. Nakatani, M; Yokoyama, N; Hatakeyama, S.J. Am. Chem. Soc. 1999, 121, 10219
Asymmetric Baylis-Hillman Iwabuchi, Y.; Nakatani, M.; Yokoyama, N.; Hatakeyama, S. J. Am. Chem. Soc. 1999, 121, 10219. (R) - 91% ee (R) - 10% ee 74% yield 58% yield N O N OMe N O N OH H O O2N O O CF3 CF3 O O CF3 OH CF3 O2N + 1 h DMF, -50 °C 10 mol% cat. High enantioselectivities (91 – 99% ee) Modest yields (31 – 58%)
Proline · Robinson annulation Intermolecular Aldol · Mannich reaction Michael addition
Proline • Robinson Annulation • Intermolecular Aldol • Mannich Reaction • Michael Addition
Asymmetric Robinson Annulation Me 3 mol% L-Proline Me Me DME 20°C.20h 100%yed,93%ee OH meso-trione p-TSOH Me O CO2H Phh N H reflux L-Proline Eder, U, Sauer, G; Wiechert, R Angew. Chem., Int Ed 1971, 10, 496 Hajos, Z G. Parrish, D.R.J. Org. Chem. 1974, 39, 1615
Asymmetric Robinson Annulation Eder, U.; Sauer, G.; Wiechert, R. Angew. Chem., Int. Ed. 1971, 10, 496. Hajos, Z. G.; Parrish, D. R. J. Org. Chem. 1974, 39, 1615. O O Me O Me PhH Me O O DMF Me O O OH 20 °C, 20 h 100% yield, 93% ee p-TsOH reflux 3 mol% L-Proline L-Proline N H CO2 H meso-trione