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5 A. Carlone, M. Marigo, C. North, A. Landa and K. A. Jørgensen,
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7 (a) T. Furukawa, Y. Goto, J. Kawazoe, E. Tokunaga,
S. Nakamura, Y. Yang, H. Du, A. Kakehi, M. Shiro and
N. Shibata, Angew. Chem., Int. Ed., 2010, 49, 1642;
(b) A.-N. Alba, X. Companyo, A. Moyano and R. Rios, Chem.–Eur.
J., 2009, 15, 7035; (c) A.-N. Alba, X. Companyo, A. Moyano and
R. Rios, Chem.–Eur. J., 2009, 15, 11095.
Scheme 2 Application transformations of Michael adduct 3a.
optimized conditions using activated Mg(0) in the presence of
Bu4N+Brꢀ (TBAB) in MeOH11e (see ESIz) gave 3-substituted
acetal 7, which was transformed into an aldehyde ester 8. It is
noteworthy that our initial attempt to form the methoxy-
carbonylmethylated product under basic conditions (Mg, TBAB,
MeOH) without protection of the aldehyde resulted in a signifi-
cantly low yield of ca. 10%.
8 D. A. Alonso, S. Kitagaki, N. Utsumi and C. F. Barbas III, Angew.
Chem., Int. Ed., 2008, 47, 4588.
9 The studies from our group: (a) J. Wang, H. Li, L.-S. Zu, W. Jiang,
H.-X. Xie, W.-H. Duan and W. Wang, J. Am. Chem. Soc., 2006,
128, 12652; (b) L.-S. Zu, H.-X. Xie, H. Li, J. Wang and W. Wang,
Adv. Synth. Catal., 2007, 349, 2660; (c) L. Zu, H. Xie, H. Li,
J. Wang, X. Yu and W. Wang, Chem.–Eur. J., 2008, 14, 6333;
(d) S.-L. Zhang, J. Li, S.-H. Zhao and W. Wang, Tetrahedron Lett.,
2010, 51, 1766; (e) H. Li, Y.-F. Ji, J. Li, S.-L. Zhang, C.-G. Yu and
W. Wang, Sci. China Chem., 2010, 53, 135; (f) S.-L. Zhang,
Y.-N. Zhang, Y.-F. Ji, H. Li and W. Wang, Chem. Commun.,
2009, 4886; (g) S.-L. Zhang, H.-X. Xie, J. Zhu, H. Li, X.-S. Zhang,
J. Li and W. Wang, Nat. Commun., 2011, 2, 1214.
10 For recent reviews on sulfone chemistry, see: (a) A.-N. R. Alba,
X. Companyo and R. Rios, Chem. Soc. Rev., 2010, 39, 2018;
(b) M. Nielsen, C. B. Jacobsen and K. A. Jørgensen, Angew.
Chem., Int. Ed., 2010, 49, 2668; (c) A. El-Awa, M. N. Noshi,
X. M. Jourdin and P. L. Fuchs, Chem. Rev., 2009, 109, 2315.
11 For selected examples of sulfones as nucleophiles in conjugate
additions: (a) L. Jiang, Q. Lei, X. Huang, H.-L. Cui, X. Zhou and
Y.-C. Chen, Chem.–Eur. J., 2011, 17, 9489; (b) M. G. Brant,
C. M. Bromba and J. E. Wulff, J. Org. Chem., 2010, 75, 6312;
(c) N. Holub, H. Jiang, M. W. Paixao, C. Tiberi and
K. A. Jørgensen, Chem.–Eur. J., 2010, 16, 4337; (d) J. L. Garcıa
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In conclusion, we have developed a new nucleophilic reagent
CMPS 1a for the direct organocatalytic asymmetric Michael
addition to a wide range of a,b-unsaturated aldehydes in
moderate to excellent yields and with high enantioselectivities.
Moreover, as demonstrated, the Michael adducts serve as
versatile building blocks in a variety of transformations. The
application of the process in the synthesis of biologically
interesting molecules is being pursued in our laboratories.
We gratefully acknowledge the financial support from the
National Natural Science Foundation of China (Grants
90813005, 21002028 and 20902022, J. Li), National S&T Major
Project, China (Grant 2011ZX09102-005-02, J. Li), the 111 Project
(Grant B07023, J. Li and W. Wang), the Fundamental Research
Funds for the Central Universities (J. Li) and East China
University of Science & Technology (W. Wang).
12 For selected examples of sulfones as electrophiles in conjugate
additions: (a) H. Li, J. Song, X. Liu and L. Deng, J. Am. Chem.
Soc., 2005, 127, 8948; (b) A. Quintard and A. Alexakis, Chem.–Eur.
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Notes and references
1 For reviews, see: (a) J. D. Connolly and R. A. Hill, Dictionary
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2 To our knowledge, only two examples can be found in the literature
in asymmetric preparation: the use of catalytic asymmetric Diels–Alder
reactions: (a) D. A. Evans, J. S. Johnson and E. J. Olhava, J. Am.
Chem. Soc., 2000, 122, 1635; (b) D. A. Evans and J. S. Johnson, J. Am.
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13 J. B. Baudin, G. Hareau and S. A. Julia, Tetrahedron Lett., 1991,
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14 For a review of diaryl prolinol ethers catalysis, see: A. Mielgo and
C. Palomo, Chem.–Asian J., 2008, 3, 922.
3 For recent reviews on enantioselective Michael addition reactions,
see: (a) Catalytic asymmetric conjugate reactions, ed. A. Cordova,
Wiley-VCH, Weinheim, Germany, 2010; (b) J. L. Vicario, E. Reyes,
D. Dadia and L. Carrillo, in Catalytic asymmetric conjugate reactions,
ed. A. Cordova, Wiley-VCH, Weinheim, Germany, 2010, ch. 6, p. 619.
15 We observed 24% yield of byproduct generated from 1a and hex-2-enal.
(a) N. A. Magomedov, P. L. Ruggiero and Y.-C. Tang, Org. Lett.,
2004, 6, 3373; (b) J.-M. Zhang, E. A. Polishchuk, J. Chen and
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16 CCDC 844031 (3j).
c
150 Chem. Commun., 2012, 48, 148–150
This journal is The Royal Society of Chemistry 2012