Table 2 Conjugate addition of various 2-aryl-substituted propanals
13 to vinyl sulfone 2 catalyzed by chiral amine 11aa
1018; (c) X. Wu, Z. Jiang, H. M. Shen and Y. Lu, Adv. Synth.
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Entry
Product/R
t/h
Yieldb (%)
eec (%)
1
2
3
4
5
6
7
8
9
p-Me
p-F
p-Br
m-Br
o-OMe
m-OMe
2-Naphthyl
1-Naphthyl
p-CN
12
12
12
12
10
12
10
18
24
93
90
87
91
93
95
91
90
76
81
75
80
80
82
80
77
86
68
11 E. Teodori, E. Baldi, S. Dei, F. Gualtieri, M. N. Romanelli,
S. Scapecchi, C. Bellucci, C. Ghelardini and R. Matucci, J. Med.
Chem., 2004, 47, 6070.
12 For earlier reports on the use of chiral auxiliary for the con-
a quaternary center, see: (a) L. A. Paquette,
a
struction of
The reactions were performed with aldehyde (0.1 mmol), vinyl
sulfone (0.05 mmol) and catalyst (0.0025 mmol) in p-fluoro-toluene
J. P. Gilday and C. S. Ra, J. Am. Chem. Soc., 1987, 109,
6858; (b) N. Nishimura and O. Mitsunobu, Tetrahedron Lett.,
2000, 41, 2945. For a recent example, see: (c) T. Hashimoto,
K. Sakata and K. Maruoka, Angew. Chem., Int. Ed., 2009, 48,
5014.
b
c
(0.8 mL) at room temperature. Isolated yield. The ee value was
determined by chiral HPLC analysis.
13 For primary amine-promoted conjugate addition of a-branched
aldehydes to nitroolefins, see: (a) M. P. Lalonde, Y. Chen and
E. N. Jacobsen, Angew. Chem., Int. Ed., 2006, 45, 6366;
(b) S. H. McCooey and S. J. Connon, Org. Lett., 2007, 9, 599.
For secondary amine-induced activation of a-branched aldehydes,
see: (c) N. Mase, R. Thayumanavan, F. Tanaka and C. F. Barbas,
III, Org. Lett., 2004, 6, 2527; (d) W. Wang, J. Wang and H. Li,
Angew. Chem., Int. Ed., 2005, 44, 1369; (e) N. S. Chowdari,
J. T. Suri and C. F. Barbas, III, Org. Lett., 2004, 6, 2507;
(f) H. Vogt, S. Vanderheiden and S. Brase, Chem. Commun.,
2003, 2448; (g) J. T. Suri, D. D. Steiner and C. F. Barbas, III,
Org. Lett., 2005, 7, 3885; (h) S. Brandes, B. Niess, M. Bella,
A. Prieto, J. Overgaard and K. A. Jorgensen, Chem.–Eur. J.,
2006, 12, 6039.
Scheme 1 Synthesis of different chiral quaternary building blocks.
Notes and references
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14 For a recent review on the use of vinyl sulfones in organocatalytic
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´
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(0 and 47% ee).
16 (a) J.-E. Backvall, R. Chinchilla, C. Najera and M. Yus, Chem.
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¨
,
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19 See ESIw for the preparation of 11a–c and 12a–c.
20 When 2-aryl-substituted vinyl sulfones were used as acceptors for
the conjugate addition, no desired product was observed.
7 (a) Z. Jiang, Z. Liang, X. Wu and Y. Lu, Chem. Commun., 2006,
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ꢀc
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