Journal of the American Chemical Society
ARTICLE
The chiral spiro copper catalysts have a novel binuclear structure,
as indicated by single-crystal X-ray diffraction analysis, ESI-MS,
and nonlinear effect studies. The 14-electron copper centers,
trans coordination model, perfectly C2-symmetric chiral pocket,
and copperÀcopper interaction in the chiral spiro catalyst allow
for efficient chiral induction in the asymmetric NÀH insertion
reactions. Our results contribute to the understanding of transi-
tion-metal-catalyzed asymmetric NÀH insertion reactions and
can be expected to allow for the design of new, efficient chiral
catalysts for other XÀH bond insertion reactions.
(a) Maier, T. C.; Fu, G. C. J. Am. Chem. Soc. 2006, 128, 4594.
(b) Chen, C.; Zhu, S.-F.; Liu, B.; Wang, L.-X.; Zhou, Q.-L. J. Am. Chem.
Soc. 2007, 129, 12616. (c) Zhu, S.-F.; Chen, C.; Cai, Y.; Zhou, Q.-L.
Angew. Chem., Int. Ed. 2008, 47, 932. (d) Zhu, S.-F.; Cai, Y.; Mao, H.-X.;
Xie, J.-H.; Zhou, Q.-L. Nat. Chem. 2010, 2, 546. (e) Zhu, S.-F.; Song,
X.-G.; Li, Y.; Cai, Y.; Zhou, Q.-L. J. Am. Chem. Soc. 2010, 132, 16374.
(f) Saito, H.; Iwai, R.; Uchiyama, T.; Miyake, M.; Miyairi, S. Chem.
Pharm. Bull. 2010, 58, 872. SÀH bond insertions:(g) Zhang, Y.-Z.; Zhu,
S.-F.; Cai, Y.; Mao, H.-X.; Zhou, Q.-L. Chem. Commun. 2009, 5362.
SiÀH bond insertions:(h) Zhang, Y.-Z.; Zhu, S.-F.; Wang, L.-X.; Zhou,
Q.-L. Angew. Chem., Int. Ed. 2008, 47, 8496. (i) Yasutomi, Y.; Suematsu,
H.; Katsuki, T. J. Am. Chem. Soc. 2010, 132, 4510. (j) Sambasivan, R.;
Ball, Z. T. J. Am. Chem. Soc. 2010, 132, 9289.
(13) For rhodium-catalyzed diastereoselective NÀH insertion for
the preparation of α-alkyl-α-amino acid derivatives, see: Taber, D. F.;
Berry, J. F.; Martin, T. J. J. Org. Chem. 2008, 73, 9334.
(14) (a) Nakamura, E.; Yoshikai, N.; Yamanaka, M. J. Am. Chem. Soc.
2002, 124, 7181. (b) Pirrung, M. C.; Liu, H.; Morehead, A. T., Jr. J. Am.
Chem. Soc. 2002, 124, 1014. (c) Taber, D. F.; You, K. K.; Rheingold, A. L.
J. Am. Chem. Soc. 1996, 118, 547. (d) Doyle, M. P.; Westrum, L. J.;
Wolthuis, W. N. E.; See, M. M.; Boone, W. P.; Bagheri, V.; Pearson,
M. M. J. Am. Chem. Soc. 1993, 115, 958.
’ ASSOCIATED CONTENT
S
Supporting Information. Crystallographic data for 8aÀc,
b
experimental procedures, analytical data for products, NMR
spectra for new compounds, and HPLC and SFC charts for
products. This material is available free of charge via the Internet
’ AUTHOR INFORMATION
(15) For examples of β-H elimination of metal carbenes, see:
(a) Taber, D. F.; Herr, R. J.; Pack, S. K.; Geremia, J. M. J. Org. Chem.
1996, 61, 2908. (b) Goto, T.; Takeda, K.; Shimada, N.; Nambu, H.;
Anada, M.; Shiro, M.; Ando, K.; Hashimoto, S. Angew. Chem., Int. Ed.
2011, 50, 6803 and references therein. Also see ref 12i.
(16) The copper precursors were prepared according to literature
procedures. See: (a) Keller, R. N.; Wycoff, H. D. Inorg. Synth. 1946, 2, 1.
(b) Kubas, G. J. Inorg. Synth. 1990, 28, 68.
(17) α-Alkyl-α-diazoesters were prepared according to known
methods. See ref 15a and: (a) Taber, D. F.; Hennessy, M. J.; Louey,
J. P. J. Org. Chem. 1992, 57, 436. (b) Peng, C.; Wang, Y.; Wang, J.-B.
J. Am. Chem. Soc. 2008, 130, 1566. (c) Li, W.; Wang, J.; Hu, X.-L.; Shen,
K.; Wang, W.-T.; Chu, Y.-Y.; Lin, L.-L.; Liu, X.-H.; Feng, X.-M. J. Am.
Chem. Soc. 2010, 132, 8532. (d) Zhang, Z.-H.; Liu, Y.-Y.; Gong, M.-X.;
Zhao, X.-K.; Zhang, Y.; Wang, J.-B. Angew. Chem., Int. Ed. 2010, 49, 1139.
(18) (a) Barton, D. H. R.; Finet, J.-P.; Khamsi, J. Tetrahedron Lett.
1989, 30, 937. (b) McKerrow, J. D.; Al-Rawi, J. M. A.; Brooks, P. Synth.
Commun. 2010, 40, 1161.
Corresponding Author
’ ACKNOWLEDGMENT
We thank the National Natural Science Foundation of China and
the National Basic Research Program of China (2010CB833300,
2011CB808600) and the “111” Project (B06005) of the Ministry of
Education of China for financial support.
’ REFERENCES
(1) For representative reviews of the preparation of optically active
α-amino acids, see: (a) Williams, R. M. In Synthesis of Optically Active
α-Amino Acids; Baldwin, J. E., Ed.; Organic Chemistry Series; Pergamon
Press: Oxford, U.K., 1989. (b) Nꢀajera, C.; Sansano, J. M. Chem. Rev.
2007, 107, 4584 and references therein.
(2) For reviews, see: (a) Doyle, M. P.; McKervey, M. A.; Ye, T.
Modern Catalytic Methods for Organic Synthesis with Diazo Compounds;
Wiley: New York, 1998; Chapter 8. (b) Moody, C. J. Angew. Chem., Int.
Ed. 2007, 46, 9148. (c) Zhang, Z.-H.; Wang, J.-B. Tetrahedron 2008,
64, 6577.
(19) Mrꢁsiꢀc, N.; Minnaard, A. J.; Feringa, B. L.; de Vries, J. G. J. Am.
Chem. Soc. 2009, 131, 8358.
(20) Tresch, S.; Niggeweg, R.; Grossmann, K. Pest Manage. Sci.
2008, 64, 1195 and references therein.
(21) Hu and co-workers provided experimental evidence for the
existence of ammonium ylide intermediates during rhodium-catalyzed
NÀH insertions by capturing them using electrophiles. See: (a) Wang,
Y.-H.; Zhu, Y.-X.; Chen, Z.-Y.; Mi, A.-Q.; Hu, W.-H.; Doyle, M. P. Org.
Lett. 2003, 5, 3923. (b) Wang, Y.-H.; Chen, Z.-Y.; Mi, A.-Q.; Hu, W.-H.
Chem. Commun. 2004, 2486. (c) Huang, H.-X.; Wang, Y.-H.;
Chen, Z.-Y.; Hu, W.-H. Adv. Synth. Catal. 2005, 347, 531. (d) Zhu, Y.-
G.; Zhai, C.-W.; Yue, Y.-L.; Yang, L.-P.; Hu, W.-H. Chem. Commun.
2009, 1362. For selected examples of the capture of oxonium ylide
intermediates generated through OÀH insertions, see:(e) Lu, C.-D.;
Liu, H.; Chen, Z.-Y.; Hu, W.-H.; Mi, A.-Q. Org. Lett. 2005, 7, 83. (f)
Huang, H.-X.; Guo, X.; Hu, W.-H. Angew. Chem., Int. Ed. 2007, 46, 1337.
(g) Guang, X.-Y.; Yang, L.-P.; Hu, W.-H. Angew. Chem., Int. Ed. 2010,
49, 2190.
(3) Yates, P. J. Am. Chem. Soc. 1952, 74, 5376.
(4) For the selected diastereoselective NÀH insertion reactions
using chiral diazo compounds or chiral NÀH donors, see: (a) Nicoud,
J.-F.; Kagan, H. B. Tetrahedron Lett. 1971, 12, 2065. (b) Moody, C.-J.;
Morfitt, C. N.; Slawin, A. M. Z. Tetrahedron: Asymmetry 2001, 12, 1657.
(c) Davis, F. A.; Fang, T.; Goswami, R. Org. Lett. 2002, 4, 1599.
(d) Burtoloso, A. C. B.; Correia, C. R. D. Tetrahedron Lett. 2004,
45, 3355. (e) Deng, Q.-H.; Xu, H.-W.; Yuen, A. W.-H.; Xu, Z.-J.; Che,
C.-M. Org. Lett. 2008, 10, 1529.
(5) García, C. F.; McKervey, M. A.; Ye, T. Chem. Commun.
1996, 1465.
(6) Buck, R. T.; Moody, C. J.; Pepper, A. G. ARKIVOC 2002, No. viii, 16.
(7) Saito, H.; Uchiyama, T.; Miyake, M.; Anada, M.; Hashimoto, S.;
Takabatake, T.; Miyairi, S. Heterocycles 2010, 81, 1149.
(8) Bachmann, S.; Fielenbach, D.; Jørgensen, K. A. Org. Biomol.
Chem. 2004, 2, 3044.
(22) Dakin, L. A.; Ong, P. C.; Panek, J. S.; Staples, R. J.; Stavropoulos,
P. Organometallics 2000, 19, 2896.
(23) For discussions of proton transfer process in NÀH insertion
reactions, see: Jiang, J.; Xu, H.-D.; Xi, J.-B.; Ren, B.-Y.; Lv, F.-P.; Guo, X.;
Jiang, L.-Q.; Zhang, Z.-Y.; Hu, W.-H. J. Am. Chem. Soc. 2011, 133,
8428.
(24) For detailed DFT calculations on proton transfer processes in
copper- or rhodium-catalyzed OÀH insertion reactions, see: Liang, Y.;
Zhou, H.-L.; Yu, Z.-X. J. Am. Chem. Soc. 2009, 131, 17783.
(25) Hansch, C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, 165.
(9) Liu, B.; Zhu, S.-F.; Zhang, W.; Chen, C.; Zhou, Q.-L. J. Am.
Chem. Soc. 2007, 129, 5834.
(10) Lee, E. C.; Fu, G. C. J. Am. Chem. Soc. 2007, 129, 12066.
(11) Hou, Z.-R.; Wang, J.; He, P.; Wang, J.; Qin, B.; Liu, X.-H.; Lin,
L.-L.; Feng, X.-M. Angew. Chem., Int. Ed. 2010, 49, 4763.
(12) For recent examples of transition-metal-catalyzed asymmetric
insertions with other XÀH bonds, see: OÀH bond insertions:
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dx.doi.org/10.1021/ja2084493 |J. Am. Chem. Soc. 2012, 134, 436–442