Organic Letters
Letter
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The necessity of an acid and anion was also observed in the
experiments (Table 1, entry 13; Table S4 in the SI). Based on this
mechanistic understanding, the acid in the Michael addition
reactions plays two important roles: (i) the protonation of the
amino acid ester catalyst and then (ii) the extraction of the proton
of the enone by the acid anion in the process of the C−C coupling
reaction. This characteristic of proton shuttling by the acid
moleculewasalsoproposedforanotherMichaeladditionreaction
in our recent study.10c
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In conclusion, we have presented the first example of
asymmetric Michael addition of photogenerated o-quinodi-
methanes to α,β-unsaturated ketones employing simple chiral
amino acid esters as the catalyst. This reaction can be successfully
applied to 3-substituted-2-cyclohexenone and provides an
efficient protocol for constructing the quaternary carbon centers.
A variety of different enones were well tolerated, providing
Michael adducts in good yields (up to 75%) and excellent
stereoselectivities (ee up to 99% ee, dr up to >19:1). The
stereoselectivity was explained by DFT calculations for transition
states of the C−C bond formation between the iminium
intermediate and o-quinodimethanes.
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ASSOCIATED CONTENT
* Supporting Information
■
S
TheSupportingInformationisavailablefreeofchargeontheACS
(8) (a) Bauer, A.; Westkamper, F.; Grimme, S.; Bach, T. Nature 2005,
436, 1139. (b) Nicewicz, D. A.; MacMillan, D. W. C. Science 2008, 322,
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Detailed experimental procedures, characterization data of
products (NMR, HRMS, etc.), spectra of products (PDF)
X-ray crystal structure of 10 (CIF)
X-ray crystal structure of 14 (CIF)
X-ray crystal structure of 9 (CIF)
(e) Muller, C.; Bauer, A.; Bach, T. Angew. Chem., Int. Ed. 2009, 48, 6640.
̈
(f) Shih, H.-W.; Vander Wal, M. N.; Grange, R. L.; MacMillan, D. W. C. J.
Am. Chem. Soc. 2010, 132, 13600. (g) Neumann, M.; Fuldner, S.; Konig,
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B.; Zeitler, K. Angew. Chem., Int. Ed. 2011, 50, 951. (h) Muller, C.; Bauer,
̈
A.; Maturi, M. M.; Cuquerella, M. C.; Miranda, M. A.; Bach, T. J. Am.
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AUTHOR INFORMATION
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́
Corresponding Author
ORCID
Fernandez, A.; Melchiorre, P. Nat. Chem. 2013, 5, 750. (j) Cecere, G.;
́
Konig, C. M.; Alleva, J. L.; MacMillan, D. W. C. J. Am. Chem. Soc. 2013,
̈
135, 11521. (k) Stevens, J. M.; MacMillan, D. W. C. J. Am. Chem. Soc.
2013, 135, 11756. (l) Arceo, E.; Bahamonde, A.; Bergonzini, G.;
Melchiorre, P. Chem. Sci. 2014, 5, 2438. (m) Riente, P.; Adams, A. M.;
Notes
̀
Albero, J.; Palomares, E.; Pericas, M. A. Angew. Chem., Int. Ed. 2014, 53,
9613. (n) Zhu, Y.; Zhang, L.; Luo, S. J. Am. Chem. Soc. 2014, 136, 14642.
(o)Alonso, R.;Bach,T.Angew. Chem., Int.Ed.2014,53,4368. (p)Maturi,
M. M.; Bach, T. Angew. Chem., Int. Ed. 2014, 53, 7661. (q) Vallavoju, N.;
Selvakumar, S.;Jockusch, S.;Sibi, M. P.;Sivaguru, J. Angew. Chem., Int. Ed.
2014, 53, 5604. (r) Silvi, M.; Arceo, E.; Jurberg, I. D.; Cassani, C.;
Melchiorre, P. J. Am. Chem. Soc. 2015, 137, 6120. (s) Welin, E. R.;
Warkentin, A. A.; Conrad, J. C.; MacMillan, D. W. C. Angew. Chem., Int.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by the National Natural Science
Foundation of China (21272068, 21572056), the Program for
New Century Excellent Talents in University (NCET-13-0800),
the Fundamental Research Funds for the Central Universities.
Ed. 2015, 54, 9668. (t) Wozniak, Ł.; Murphy, J. J.; Melchiorre, P. J. Am.
́
Chem. Soc. 2015, 137, 5678. (u) Bahamonde, A.; Melchiorre, P. J. Am.
Chem. Soc. 2016, 138, 8019.
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