Organic Letters
Letter
Leppkes, R.; Winkler, J.; Zimmerman, S. J. Am. Chem. Soc. 1986, 108,
1969. (j) Breslow, R.; Chmielewski, J.; Foley, D.; Johnson, B.; Kumabe,
N.; Varney, M.; Mehra, R. Tetrahedron 1988, 44, 5515. (k) Ando, M.;
Kuzuhara, H. Bull. Chem. Soc. Jpn. 1989, 62, 244. (l) Ando, M.;
Kuzuhara, H. Bull. Chem. Soc. Jpn. 1990, 63, 1925. (m) Fasella, E.; Dong,
S. D.; Breslow, R. Bioorg. Med. Chem. 1999, 7, 709. (n) Zhou, W.; Yerkes,
N.; Chruma, J. J.; Liu, L.; Breslow, R. Bioorg. Med. Chem. Lett. 2005, 15,
1351. (o) Bandyopadhyay, S.; Zhou, W.; Breslow, R. Org. Lett. 2007, 9,
1009. (p) Breslow, R.; Wei, S.; Kenesky, C. Tetrahedron 2007, 63, 6317.
(q) Wei, S.; Wang, J.; Venhuizen, S.; Skouta, R.; Breslow, R. Bioorg. Med.
Chem. Lett. 2009, 19, 5543.
(5) For references on asymmetric transamination of α-keto acids with
pyridoxamine catalyzed by chiral Lewis acids, see: (a) Bernauer, K.;
Deschenaux, R.; Taura, T. Helv. Chim. Acta 1983, 66, 2049.
(b) Deschenaux, R.; Bernauer, K. Helv. Chim. Acta 1984, 67, 373.
(6) Svenson, J.; Zheng, N.; Nicholls, I. A. J. Am. Chem. Soc. 2004, 126,
8554.
(7) For references on asymmetric transamination of α-keto acids in the
presence of a supramolecular catalyst, see: (a) Kikuchi, J.-i.; Zhang, Z.-
Y.; Murakami, Y. Chem. Lett. 1994, 23, 1559. (b) Kikuchi, J.-i.; Zhang, Z.-
Y.; Murakami, Y. J. Am. Chem. Soc. 1995, 117, 5383.
(8) For references on catalytic asymmetric transamination of α-keto
acids in the presence of a semisynthetic transaminase, see: (a) Qi, D.;
Kuang, H.; Distefano, M. D. Bioorg. Med. Chem. Lett. 1998, 8, 875.
the imino C−H of 19 is the rate-determining step for the
transamination.
In summary, we have developed a class of novel chiral
pyridoxals 8−9 starting from pyridoxine and (S)-α,α-diary-
lprolinols, which displayed high catalytic activity and good
enantioselectivity in the transamination of α-keto acids to give
various optically active α-amino acids in 29−85% yields with 53−
80% ee’s under mild conditions. This work represents the first
chiral-pyridoxal-catalyzed asymmetric biomimetic transamina-
tion of α-keto acids involving two half-transaminations and
serves as an impressive example for the application of pyridoxals
in asymmetric catalysis. Further studies on detailed mechanisms,
developing more efficient catalysts, and expanding catalysis
applications of chiral pyridoxals are underway.
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
Procedures for synthesis of compounds 8−9 and trans-
amination of α-keto acids, characterization data, and NMR
spectra along with HPLC chromatograms (PDF)
(b) Haring, D.; Distefano, M. D. Bioconjugate Chem. 2001, 12, 385.
̈
(9) For leading references on asymmetric transamination of ketones
catalyzed or mediated by chiral bases or Lewis acids, see: (a) Soloshonok,
V. A.; Kirilenko, A. G.; Galushko, S. V.; Kukhar, V. P. Tetrahedron Lett.
1994, 35, 5063. (b) Willems, J. G. H.; de Vries, J. G.; Nolte, R. J. M.;
Zwanenburg, B. Tetrahedron Lett. 1995, 36, 3917. (c) Soloshonok, V. A.;
Ono, T. J. Org. Chem. 1997, 62, 3030. (d) Xiao, J.; Zhang, X.; Yuan, C.
Heteroat. Chem. 2000, 11, 536. (e) Hjelmencrantz, A.; Berg, U. J. Org.
Chem. 2002, 67, 3585. (f) Knudsen, K. R.; Bachmann, S.; Jørgensen, K.
A. Chem. Commun. 2003, 2602. (g) Bachmann, S.; Knudsen, K. R.;
Jørgensen, K. A. Org. Biomol. Chem. 2004, 2, 2044. (h) Soloshonok, V.
A.; Yasumoto, M. J. Fluorine Chem. 2007, 128, 170. (i) Xiao, X.; Xie, Y.;
Su, C.; Liu, M.; Shi, Y. J. Am. Chem. Soc. 2011, 133, 12914. (j) Wu, Y.;
Deng, L. J. Am. Chem. Soc. 2012, 134, 14334. (k) Xie, Y.; Pan, H.; Xiao,
X.; Li, S.; Shi, Y. Org. Biomol. Chem. 2012, 10, 8960. (l) Pan, H.; Xie, Y.;
Liu, M.; Shi, Y. RSC Adv. 2014, 4, 2389. (m) Su, C.; Xie, Y.; Pan, H.; Liu,
M.; Tian, H.; Shi, Y. Org. Biomol. Chem. 2014, 12, 5856.
(10) (a) Liu, L.; Zhou, W.; Chruma, J.; Breslow, R. J. Am. Chem. Soc.
2004, 126, 8136. (b) Chruma, J. J.; Liu, L.; Zhou, W.; Breslow, R. Bioorg.
Med. Chem. 2005, 13, 5873.
(11) (a) Ding, L.; Chen, J.; Hu, Y.; Xu, J.; Gong, X.; Xu, D.; Zhao, B.; Li,
H. Org. Lett. 2014, 16, 720. (b) Liu, X.; Gao, A.; Ding, L.; Xu, J.; Zhao, B.
Org. Lett. 2014, 16, 2118. (c) Xu, J.; Chen, J.; Yang, Q.; Ding, L.; Liu, X.;
Xu, D.; Zhao, B. Adv. Synth. Catal. 2014, 356, 3219.
AUTHOR INFORMATION
Corresponding Author
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We are grateful for the generous financial support from the
Program of the Professor of Special Appointment (Eastern
Scholar) at Shanghai Institutions of Higher Learning, NSFC
(21272158, 21472125), the Program for New Century Excellent
Talents in University (NECT-12-1054), and PCSIRT
(IRT1269).
REFERENCES
■
(1) For selected reviews on enzymatic transamination, see: (a) Zhu, D.;
Hua, L. Biotechnol. J. 2009, 4, 1420. (b) Ward, J.; Wohlgemuth, R. Curr.
Org. Chem. 2010, 14, 1914. (c) Koszelewski, D.; Tauber, K.; Faber, K.;
Kroutil, W. Trends Biotechnol. 2010, 28, 324.
(12) (a) Regla, I.; Luna, H.; Per
Zaldívar, V.; Calcagno, M. L. Tetrahedron: Asymmetry 2004, 15, 1285.
(b) Suarez, R. M.; Perez Sestelo, J.; Sarandeses, L. A. Org. Biomol. Chem.
2004, 2, 3584.
́
ez, H. I.; Demare, P.; Bustos-Jaimes, I.;
(2) For reviews on biomimetic transamination, see: (a) Breslow, R. Acc.
Chem. Res. 1995, 28, 146. (b) Murakami, Y.; Kikuchi, J.-i.; Hisaeda, Y.;
Hayashida, O. Chem. Rev. 1996, 96, 721. (c) Han, J.; Sorochinsky, A. E.;
Ono, T.; Soloshonok, V. A. Curr. Org. Synth. 2011, 8, 281. (d) So, S. M.;
Kim, H.; Mui, L.; Chin, J. Eur. J. Org. Chem. 2012, 2012, 229. (e) Xie, Y.;
Pan, H.; Liu, M.; Xiao, X.; Shi, Y. Chem. Soc. Rev. 2015, 44, 1740.
(3) (a) Metzler, D. E.; Snell, E. E. J. Am. Chem. Soc. 1952, 74, 979.
(b) Metzler, D. E.; Ikawa, M.; Snell, E. E. J. Am. Chem. Soc. 1954, 76, 648.
(c) Matsuo, Y. J. Am. Chem. Soc. 1957, 79, 2016. (d) Bruice, T. C.;
Topping, R. M. J. Am. Chem. Soc. 1963, 85, 1480.
(4) For leading references on asymmetric transamination of α-keto
acids with stoichiometric chiral pyridoxamine analogues, see:
(a) Kuzuhara, H.; Komatsu, T.; Emoto, S. Tetrahedron Lett. 1978, 19,
3563. (b) Breslow, R.; Hammond, M.; Lauer, M. J. Am. Chem. Soc. 1980,
102, 421. (c) Tachibana, Y.; Ando, M.; Kuzuhara, H. Chem. Lett. 1982,
11, 1765. (d) Tachibana, Y.; Ando, M.; Kuzuhara, H. Chem. Lett. 1982,
11, 1769. (e) Breslow, R.; Czarnik, A. W. J. Am. Chem. Soc. 1983, 105,
1390. (f) Zimmerman, S. C.; Czarnik, A. W.; Breslow, R. J. Am. Chem.
Soc. 1983, 105, 1694. (g) Tachibana, Y.; Ando, M.; Kuzuhara, H. Bull.
Chem. Soc. Jpn. 1983, 56, 3652. (h) Zimmerman, S. C.; Breslow, R. J. Am.
Chem. Soc. 1984, 106, 1490. (i) Breslow, R.; Czarnik, A. W.; Lauer, M.;
́
́
(13) Sun, S.; Zabinski, R. F.; Toney, M. D. Biochemistry 1998, 37, 3865.
(14) (a) Olivard, J.; Metzler, D. E.; Snell, E. E. J. Biol. Chem. 1952, 199,
669. (b) Liu, L.; Breslow, R. Tetrahedron Lett. 2001, 42, 2775.
(15) (a) Gansow, O. A.; Holm, R. H. J. Am. Chem. Soc. 1969, 91, 5984.
(b) Banks, B. E. C.; Diamantis, A. A.; Vernon, C. A. J. Chem. Soc. 1961,
4235. (c) Abbott, E. H.; Martell, A. E. J. Am. Chem. Soc. 1969, 91, 6931.
(d) Kubala, G.; Martell, A. E. J. Am. Chem. Soc. 1983, 105, 449.
(16) (a) Liao, R.-Z.; Ding, W.-J.; Yu, J.-G.; Fang, W.-H.; Liu, R.-Z. J.
Comput. Chem. 2008, 29, 1919. (b) Tachibana, Y.; Ando, M.; Kuzuhara,
H. Bull. Chem. Soc. Jpn. 1983, 56, 2263.
(17) Blake, M. I.; Siegel, F. P.; Katz, J. J.; Kilpatrick, M. J. Am. Chem. Soc.
1963, 85, 294.
D
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