Journal of the American Chemical Society
Communication
(6) For reviews on bisoxazoline/Cu(II), see: (a) Ghosh, A. K.;
Packiarajan, M.; Cappiello, J. Tetrahedron: Asymmetry 1998, 9, 1.
(b) Desimoni, G.; Faita, G.; Jørgensen, K. A. Chem. Rev. 2011, 111,
PR284. For selected recent studies, see: (c) Foltz, C.; Stecker, B.;
Marconi, G.; Bellemin-Laponnaz, S.; Wadepohl, H.; Gade, L. H.
Chem.Eur. J. 2007, 13, 9912. (d) Landa, A.; Richter, B.; Johansen, R.
L.; Minkkila, A.; Jørgensen, K. A. J. Org. Chem. 2007, 72, 240.
(e) Singh, P. K.; Bisai, A.; Singh, V. K. Tetrahedron Lett. 2007, 48,
1127. (f) Toussaint, A.; Pfaltz, A. Eur. J. Org. Chem. 2008, 4591.
(g) Hager, M.; Wittmann, S.; Schatz, A.; Pein, F.; Kreitmeier, P.;
Reiser, O. Tetrahedron: Asymmetry 2010, 21, 1194. (h) Harvey, J. S.;
Simonovich, S. P.; Jamison, C. R.; MacMillan, D. W. C. J. Am. Chem.
Soc. 2011, 133, 13782. (i) Bigot, A.; Williamson, A. E.; Gaunt, M. J. J.
Am. Chem. Soc. 2011, 133, 13778. (j) Nano, A.; Brelot, L.; Rogez, G.;
Maisse-Francois, A.; Bellemin-Laponnaz, S. Inorg. Chim. Acta 2011,
376, 285. (k) Leboeuf, D.; Gandon, V.; Ciesielski, J.; Frontier, A. J. J.
Am. Chem. Soc. 2012, 134, 6296. (l) Li, J.; Pan, W.; Wang, Z.; Zhang,
X.; Ding, K. Adv. Synth. Catal. 2012, 354, 1980. (m) Deng, C.; Wang,
L. J.; Zhu, J.; Tang, Y. Angew. Chem., Int. Ed. 2012, 51, 11620.
(n) Song, X.-G.; Zhu, S.-F.; Xie, X. L.; Zhou, Q.-L. Angew. Chem., Int.
Ed. 2013, 52, 2555. (o) Xiong, H.; Xu, H.; Liao, S.; Xie, Z.; Tang, Y. J.
Am. Chem. Soc. 2013, 135, 7851.
of the products by comparing their optical rotations with the
literature values; other products were assigned by analogy.
In summary, the asymmetric intramolecular Cannizzaro
reaction of glyoxals has been realized for the first time with
high efficiency and high levels of enantioselectivity by
combining TOX/copper catalysis with a slow substrate-release
protocol. The catalytic system is mild and efficient, and
compatible with both aryl- and alkylglyoxals, allowing a facile
access to a variety of α-hydroxy carboxylic acid derivatives with
high optical purity. Preliminary results suggested that the high
enantioselectivity observed in the present reaction was mainly
dominated by the catalyst-controlled face-selective addition of
alcohols to coordinated glyoxals. Further mechanistic study and
the extension of the present catalytic system to other redox and
1,2-shift reactions are currently in progress in our laboratory.
ASSOCIATED CONTENT
* Supporting Information
■
S
Experimental procedures, characterizations, analytical data of
products, and spectra of NMR and HPLC. This material is
(7) For reviews, see: (a) Zhou, J.; Tang, Y. Chem. Soc. Rev. 2005, 34,
664. (b) Bellemin-Laponnaz, S.; Gade, L. H. Actual Chimique 2007, 16.
(c) Hargaden, G. C.; Guiry, P. J. Chem. Rev. 2009, 109, 2505. For
selected examples, see: (d) Zhou, J.; Tang, Y. J. Am. Chem. Soc. 2002,
124, 9030. (e) Rasappan, R.; Hager, M.; Gissible, A.; Reiser, O. Org.
Lett. 2006, 8, 6099. (f) Seitz, M.; Capacchione, C.; Bellemin-Laponnaz,
S.; Wadepohl, H.; Ward, B. D.; Gade, L. H. Dalton Trans. 2006, 193.
(g) Gade, L. H.; Bellemin-Laponnaz, S. Chem.Eur. J. 2008, 14, 4142.
AUTHOR INFORMATION
Corresponding Authors
■
Notes
(h) Schatz, A.; Rasappan, R.; Hager, M.; Gissibl, A.; Reiser, O.
̈
The authors declare no competing financial interest.
Chem.Eur. J. 2008, 14, 7259. (i) Rendina, V. L.; Moebius, D. C.;
Kingsbury, J. S. Org. Lett. 2011, 13, 2004. (j) Rendina, V. L.; Kaplan,
H. Z.; Kingsbury, J. S. Synthesis 2012, 44, 686. (k) Li, J.; Liao, S.-H.;
Xiong, H.; Zhou, Y.-Y.; Sun, X.-L.; Zhang, Y.; Zhou, X.-G.; Tang, Y.
Angew. Chem., Int. Ed. 2012, 51, 8838. (l) Xu, H.; Qu, J.-P.; Liao, S.;
Xiong, H.; Tang, Y. Angew. Chem., Int. Ed. 2013, 52, 4004. (m) Zhou,
Y.-Y.; Li, J.; Ling, L.; Liao, S.-H.; Sun, X.-L.; Li, Y.-X.; Wang, L.-J.;
Tang, Y. Angew. Chem., Int. Ed. 2013, 52, 1452. (n) Zhou, J.-L.; Wang,
L.-J.; Xu, H.; Sun, X.-L.; Tang, Y. ACS Catal. 2013, 3, 685.
(8) For details, please see the Supporting Information.
ACKNOWLEDGMENTS
■
We are grateful for the financial support from the National
Natural Sciences Foundation of China (20932008, 21121062,
and 21072207), the Major State Basic Research Development
Program (Grant No. 2009CB825300), and the Chinese
Academy of Sciences.
(9) Ohshima, T.; Yamamoto, Y.; Takaki, U.; Inoue, Y.; Saeki, T.;
Itou, K.; Maegawa, Y.; Iwasaki, T.; Mashima, K. Chem. Commun. 2009,
2688.
(10) As reaction 4 also delivered the (S)-configured product, albeit
with very low selectivity, a slight enhancement of the enantioselectivity
by the DKR process is also possible.
(11) (a) Knifton, J. F. Tetrahedron Lett. 1975, 2163. (b) Knifton, J. F.
J. Org. Chem. 1976, 41, 1200. (c) Mashima, K.; Kusano, K. H.; Sato,
N.; Matsumura, Y.; Nozaki, K.; Kumobayashi, H.; Sayo, N.; Hori, Y.;
Ishizaki, T.; Akutagawa, S.; Takaya, H. J. Org. Chem. 1994, 59, 3064.
(d) Li, Y.-J.; Izumi, T. J. Chin. Chem. Soc. 2002, 49, 505. (e) Schabel,
T.; Belger, C.; Plietker, B. Org. Lett. 2013, 15, 2858.
(12) (a) Valls, N.; Vallribera, M.; Carmeli, S.; Bonjoch, J. Org. Lett.
2003, 5, 447. (b) Henke, B. R. J. Med. Chem. 2004, 47, 4118.
(c) Shrestha, S.; Bhattarai, B. R.; Cho, H.; Choi, J. K.; Cho, H. Bioorg.
Med. Chem. Lett. 2007, 17, 2728.
REFERENCES
■
(1) (a) Pechmann, H. v. Ber. Dtsch. Chem. Ges. 1887, 20, 2904.
(b) Fuson, R. C.; Gray, H.; Gouza, J. J. J. Am. Chem. Soc. 1939, 61,
1937. (c) Alexander, E. R. J. Am. Chem. Soc. 1947, 69, 289.
(d) Salomaa, P. Acta Chem. Scand. 1956, 10, 311.
(2) (a) Jin, S. J.; Arora, P. K.; Sayre, L. M. J. Org. Chem. 1990, 55,
3011. (b) Likhar, P. R.; Bandyopadhyay, A. K. Synlett 2000, 538.
(c) Abaee, M. S.; Sharifi, R.; Mojtahedi, M. M. Org. Lett. 2005, 7, 5893.
(d) Curini, M.; Epifano, F.; Genovese, S.; Marcotullio, M. C.; Rosati,
O. Org. Lett. 2005, 7, 1331. (e) Hayashi, Y.; Sasaki, Y. Chem. Commun.
2005, 2716. (f) Wang, Z.-C.; Jiang, Y.-J.; Baiker, A.; Huang, J. Acs
Catal 2013, 3, 1573.
(3) (a) Hanessian, S. Total Synthesis of Natural Products: The Chiron
Approach; Pergamon: New York, 1983. (b) Coppola, G. M.; Schuster,
H. F. α-Hydroxy Acids in Enantioselective Syntheses; Wiley-VCH:
Weinheim, 1997. (c) Yang, J.-W.; List, B. Org. Lett. 2006, 8, 5653.
(d) Sun, X.-F.; Li, W.; Zhou, L.; Zhang, X.-M. Chem.Eur. J. 2009,
15, 7302. (e) Li, S.; Zhu, S.-F.; Xie, J.-H.; Song, S.; Zhang, C.-M.;
Zhou, Q.-L. J. Am. Chem. Soc. 2010, 132, 1172. (f) Zhu, S.-F.; Zhou,
Q.-L. Acc. Chem. Res. 2012, 45, 1365.
(4) (a) Maruyama, K.; Murakami, Y.; Yoda, K.; Mashino, T.;
Nishinaga, A. J. Chem. Soc., Chem. Commun. 1992, 1617. (b) Russell, A.
E.; Miller, S. P.; Morken, J. P. J. Org. Chem. 2000, 65, 8381.
(c) Ishihara, K.; Yano, T.; Fushimi, M. J. Fluorine Chem. 2008, 129,
994.
(5) An elegant biomimetic approach via dienol mechansim afforded
35% yield and up to 83% ee: Schmitt, E.; Schiffers, I.; Bolm, C.
Tetrahedron Lett. 2009, 50, 3185.
16852
dx.doi.org/10.1021/ja409859x | J. Am. Chem. Soc. 2013, 135, 16849−16852