Asymmetric Michael Addition of Aromatic Ketones
Letters in Organic Chemistry, 2010, Vol. 7, No. 5
371
[3]
For recent reviews on organocatalytic Michael additions, see: (a)
Sulzer-Mossé, S.; Alexakis, A. Chiral amines as organocatalysts for
asymmetric conjugate addition to nitroolefins and vinyl sulfones
via enamine activation. Chem. Commun., 2007, 3123-3135; (b)
Almasi, D; Alonso, D.A.; Najera, C. Organocatalytic asymmetric
conjugate additions. Tetrahedron Asymmetry, 2007, 18, 299-365;
(c) Tsogoeva, S.B. Recent advances in asymmetric organocatalytic
1,4-conjugate additions. Eur. J. Org. Chem., 2007, 1701-1716; (d)
Vicario, J.L.; Badía, D.; Carrillo, L. Organocatalytic
enantioselective michael and hetero-michael reactions. Synthesis,
2007, 2065-2092.
J = 12.6, 9.0 Hz, 1H), 4.25-4.15 (m, 1H) 3.44-3.41 (m, 2H);
13C NMR (75M, CDCl3): ꢀ 196.4, 138.1, 136.2, 133.6, 132.1,
129.2, 128.8, 127.9, 121.8, 79.2, 41.3, 38.7 ppm. IR(KBr): ꢁ
3349, 3083, 2958, 2921, 1683, 1537, 1488, 1424, 1371,
1269, 1231, 1010, 825, 771, 753, 690, 628, 571 cm-1. HRMS
(ESI-TOF) calcd for C16H14BrNNaO3 ([M+Na]+)
370.0052, Found 370.0049.
=
Compound (S)-4i
White solid; 90% yield; 1H NMR (300 M, CDCl3): ꢀ 7.93
(d. J = 7.5 Hz, 2H), 7.58-7.56 (m, 1H), 7.49-7.43 (m, 2H),
7.31-7.26 (m, 1H), 7.09-6.97 (m, 3H), 4.84(dd, J = 12.6, 6.6
Hz, 1H), 4.68 (dd, J = 12.6, 8.1 Hz, 1H), 4.29-4.21 (m, 1H),
3.49-3.42 (m, 2H).13C NMR (300 M, CDCl3): ꢀ 196.4, 164.6,
141.6, 136.2, 133.6, 130.7, 129.1, 128.7, 127.9, 123.2, 115.0,
79.2, 41.3, 38.9 ppm. IR (KBr): ꢁ 3361, 3062, 2919, 1687,
1614, 1546, 1487, 1449, 1368, 1269, 1225, 1149, 1002, 893,
794, 701, 685, 624 cm-1. HRMS (ESI-TOF) calcd for
C16H14FNNaO3 ([M+Na]+) = 310.0853, Found 310.0850.
[4]
For recent reviews on organocatalysis, see: (a) Berkessel, A.;
Gröger, H. Asymmetric Organocatalysis; Wiley-VCH: Weinheim,
2005; (b) Dalko, P.I. Enantioselective Organocatalysis: Reactions
and Experimental Procedures; Wiley-VCH: Weinheim, 2007; (c)
Pellissier, H. Asymmetric organocatalysis. Tetrahedron, 2007, 63,
9267-9331; (d) special issue on organocatalysis: List, B.
introduction: organocatalysis. Chem. Rev., 2007, 107, 5413-5415;
(e) Figueiredo, R.M.; Christmann, M. Organocatalytic synthesis of
drugs and bioactive natural products. Eur. J. Org. Chem., 2007,
2575-2600; (f) Dondoni, A.; Massi, A. Asymmetric
organocatalysis: from infancy to adolescence. Angew. Chem. Int.
Ed. Engl., 2008, 47, 4638-4660; (g) Kotsuki , H.; Ikishima, H.;
Okuyama, A. Organocatalytic asymmetric synthesis using proline
and related molecules. Part 1. Heterocycles, 2008, 75, 493-529; (h)
Kotsuki, H.; Ikishima, H.; Okuyama, A. Organocatalytic
asymmetric synthesis using proline and related molecules. Part 2.
Heterocycles, 2008, 75, 757-797; (i) Melchiorre, P.; Marigo, M.;
Carlone, A.; Bartoli, G. Asymmetric aminocatalysis - gold rush in
organic chemistry. Angew. Chem. Int. Ed. Engl., 2008, 47, 6138-
6171; (j) Bertelsen. S.; Jørgensen. K.A. Organocatalysis—after the
gold rush. Chem. Soc. Rev., 2009, 38, 2178-2189.
Compound (S)-4o
1
Oil; 76% yield; H NMR (300 M, CDCl3): ꢀ 7.87-7.77
(m, 2H), 7.52-7.26 (m, 7H), 4.82 (dd, J = 12.3, 6.9 Hz, 1H),
4.69 (dd, J = 12.3, 7.8 Hz, 1H), 4.26-4.17 (m, 1H), 3.48-3.36
(m, 2H) ppm; 13C NMR (300 M, CDCl3): ꢀ 195.6, 138.8,
137.9, 135.1, 133.4, 130.0, 129.1, 128.1, 127.9, 127.6, 126.0,
79.4, 41.6, 39.2 ppm. IR (KBr): ꢁ 3066, 3031, 1689, 1551,
1454, 1425, 1378, 1203, 1078, 999, 784, 765, 700, 680 cm-1.
HRMS (ESI-TOF) calcd for C16H14ClNNaO3 ([M+Na]+) =
326.0560, Found 326.0554.
[5]
[6]
List, B.; Lerner, R.A.; Barbas, C.F., III. Proline-catalyzed direct
asymmetric aldol reactions. J. Am.Chem. Soc., 2000, 122, 2395-
2396
For reviews on bifunctional thiourea-based organocatalysis, see: (a)
Takemoto, Y. Recognition and activation by ureas and thioureas:
stereoselective reactions using ureas and thioureas as hydrogen-
bonding donors. Org. Biomol. Chem., 2005, 3, 4299-4306; (b)
Connon, S.J. Organocatalysis mediated by (Thio)urea derivatives.
Chem.-Eur. J., 2006, 12, 5418-5427; (c) Taylor, M.S.; Jacobsen,
E.N. Asymmetric catalysis by chiral hydrogen-bond donors.
Angew. Chem. Int. Ed. Engl., 2006, 45, 1520-1543.
For selected reviews on enamine catalysis, see: (a) List, B.
Enamine catalysis is a powerful strategy for the catalytic generation
and use of carbanion equivalents. Acc. Chem. Res., 2004, 37, 548-
557; (b) Notz, W.; Tanaka, F.; Barbas, C.F., III. Enamine-based
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Mukherjee, S.; Yang, J.-W.; Hoffmann, S.; List, B. Asymmetric
enamine catalysis. Chem. Rev., 2007, 107, 5471-5569.
Compound (S)-4q
Oil; 81% yield; 1H NMR (300 M, CDCl3): ꢀ 8.03 (s, 1H),
7.84-7.67 (m, 2H), 7.36-7.26 (m, 6H), 4.82 (dd, J = 12.3,
6.9Hz, 1H), 4.69 (dd, J = 12.3, 7.5Hz, 1H), 4.26-4.16 (m,
1H),3.43-3.41 (m, 2H) ppm; 13C NMR (300 M, CDCl3): ꢀ
195.5, 138.8, 138.0, 136.4, 131.1, 130.3, 129.1, 127.9, 127.4,
126.5, 123.0, 79.4, 41.6, 39.2 ppm. IR (KBr): ꢁ 3064, 3031,
2917, 1688, 1551, 1422, 1378, 1224, 1201, 1068, 955, 783,
763, 700, 680 cm.-1 HRMS (ESI-TOF) calcd for
C16H14BrNNaO3 ([M+Na]+) = 370.0043, Found 370.0049.
[7]
[8]
For selected examples on hydrogen bond activation, see: (a) Yoon,
T.P.; Jacobsen, E.N. Highly enantioselective thiourea-catalyzed
nitro-mannich reactions. Angew. Chem. Int. Ed. Engl., 2005, 44,
466-468; (b) Wenzel, A.G.; Jacobsen, E.N. asymmetric catalytic
mannich reactions catalyzed by urea derivatives: enantioselective
synthesis of ꢃ-aryl-ꢃ-amino acids. J. Am. Chem. Soc., 2002, 124,
12964-12965; (c) Liu, T.-Y.; Cui, H.-L.; Long, J.; Li, B.-J.; Wu,
Y.; Ding, L.-S.; Chen, Y.-C. organocatalytic and highly
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Soc., 2007, 129, 1878-1879; (d) Song, J.; Shih, H.-W.; Deng, L.
Asymmetric mannich reactions with in situ generation of
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2007, 9, 603-606; (e) Wenzel, A.G.; Lalonde, M. P.; Jacobsen,
E.N. Divergent stereoinduction mechanisms in urea-catalyzed
additions to imines. Synlett., 2003, 1919-1922; (f) Wang, C.-J.;
Dong, X.-Q.; Zhang, Z.-H.; Xue, Z.-Y.; Teng, H.-L. Highly anti-
selective asymmetric nitro-mannich reactions catalyzed by
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(i) Okino, T.; Nakamura, S.; Furukawa, T.; Takemoto, Y.
ACKNOWLEDGEMENTS
We are grateful for the financial support from National
Natural Science Foundation of China (20802075) and the
Chinese Academy of Sciences.
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