6
664
H. Saito et al. / Tetrahedron Letters 53 (2012) 6662–6664
87. These data include MOL files and InChiKeys of the most impor-
tant compounds described in this article.
References and notes
1.
For general reviews of the reaction of a-diazocarbonyl compounds: (a) Ye, T.;
McKervey, M. A. Chem. Rev. 1994, 94, 1091; (b) Doyle, M. P.; McKervey, M. A.;
Ye, T. Modern Catalytic Methods for Organic Synthesis with Diazo Compounds;
Wiley-Interscience: New York, 1998. 433; (c) Zhang, Z.; Wang, J. Tetrahedron
2008, 64, 6577.
2
.
.
For a review on the asymmetric NꢀH insertion reaction: (a) Moody, C. J. Angew.
Chem., Int. Ed. 2007, 46, 9148; For selected examples of diastereoselective NꢀH
insertions (b) Nicoud, J.-F.; Kagan, H. B. Tetrahedron Lett. 1971, 2065; (c) Taber,
D. F.; Berry, J. F.; Martin, T. J. J. Org. Chem. 2008, 73, 9334.
3
Asymmetric NꢀH insertion with
a copper complex: (a) Bachmann, S.;
Fielenbach, D.; Jørgensen, K. A. Org. Biomol. Chem. 2004, 2, 3044; (b) Liu, B.;
Zhu, S.-F.; Zhang, W.; Chen, C.; Zhou, Q.-L. J. Am. Chem. Soc. 2007, 129, 5834; (c)
Lee, E. C.; Fu, G. C. J. Am. Chem. Soc. 2007, 129, 12066; (d) Hou, Z.; Wang, J.; He,
P.; Wang, J.; Qin, B.; Liu, X.; Lin, L.; Feng, X. Angew. Chem., Int. Ed. 2010, 49,
4763; (e) Zhu, S.-F.; Xu, B.; Wang, G.-P.; Zhou, Q.-L. J. Am. Chem. Soc. 2012, 134,
436.
4
.
.
Asymmetric NꢀH insertion with
a rhodium complex: (a) García, C. F.;
McKervey, M. A.; Ye, T. Chem. Commun. 1996, 1465; (b) Buck, R. T.; Moody, C.
J.; Pepper, A. G. ARKIVOC 2002, No. viii, 16.; (c) Saito, H.; Uchiyama, T.; Miyake,
M.; Anada, M.; Hashimoto, S.; Takabatake, T.; Miyairi, S. Heterocycles 2010, 81,
1149; (d) Xu, B.; Zhu, S.-F.; Xie, X.-L.; Shen, J.-J.; Zhou, Q.-L. Angew. Chem., Int.
Ed. 2011, 50, 11483.
Scheme 3.
5
(a) Hashimoto, S.; Watanabe, N.; Ikegami, S. J. Chem. Soc. Chem. Commun. 1992,
1
2
508; (b) Hashimoto, S.; Watanabe, N.; Ikegami, S. Tetrahedron Lett. 1992, 33,
709.
are unclear at the present time and warrant additional studies. The
product yield and enantioselectivity obtained with O-methyldihy-
6. Jiang, J.; Xu, H.-D.; Xi, J.-B.; Ren, B.-Y.; Lv, F.-P.; Guo, X.; Jiang, L.-Q.; Zhang, Z.-Y.;
1
6
Hu, W.-H. J. Am. Chem. Soc. 2011, 133, 8428.
So, S. S.; Mattson, A. E. J. Am. Chem. Soc. 2012, 134, 8798.
(a) Hiratake, J.; Yamamoto, Y.; Oda, Y. J. Chem. Soc. Chem. Commun 1985, 1717;
(b) Bolm, C.; Schffers, I.; Dinter, C. L.; Gerlach, A. J. Org. Chem. 2000, 65, 6984; (c)
Lou, S.; Taoka, B. M.; Ting, A.; Schaus, S. E. J. Am. Chem. Soc. 2005, 127, 11256;
drocinchonine
decrease in enantioselectivity compared with dihydrocinchonine
4a) suggests the participation of the secondary hydroxyl group
was 44% and 6%, respectively. This dramatic
7
8
.
.
(
for the enantiomeric induction. The proposed transition states in
Scheme 2 could be used to explain the stereochemistry of the
product.
(
d) Török, B.; Abid, M.; London, G.; Esquibel, J.; Török, M.; Mhadgut, S. C.; Yan,
P.; Prakash, G. K. S. Angew. Chem., Int. Ed. 2005, 44, 3086.
(a) O’Donnell, M. J.; Bennett, W. D.; Wu, S. J. Am. Chem. Soc. 1989, 111, 2353; (b)
Iwabuchi, Y.; Nakatani, M.; Yokoyama, N.; Hatakeyama, S. J. Am. Chem. Soc.
9.
In summary, we have demonstrated that a new catalytic system
of cinchona alkaloids is effective for enantiocontrol in thermally
induced intermolecular NꢀH insertion reactions of phenyldiazoac-
etates with anilines. Our results should contribute to the under-
standing of asymmetric XꢀH (X = N, O, S) insertion reactions via
carbene intermediates. Additional studies to elucidate the reaction
mechanism and determine the origin of the stereochemical
outcome are in progress. Further studies on the efficient thermally
induced XꢀH (X = N, O, S) insertion by organocatalysts are also in
progress.
1999, 121, 10219; (c) Hang, J.; Tian, S.-K.; Tang, L.; Deng, L. J. Am. Chem. Soc.
2001, 123, 12696; (d) Tian, S.-K.; Hong, R.; Deng, L. J. Am. Chem. Soc. 2003, 125,
9900; (e) Ooi, T.; Maruoka, K. Angew. Chem., Int. Ed. 2007, 46, 4222.
10. Saito, H.; Iwai, R.; Uchiyama, T.; Miyake, M.; Miyairi, S. Chem. Pharm. Bull. 2010,
8, 872.
1. For selected examples of asymmetric OꢀH insertion of
5
1
a-diazocarbonyl
compounds by metal complexes: (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.; Song, X.-G.; Li, Y.; Cai, Y.; Zhou, Q.-L.
J. Am. Chem. Soc. 2010, 132, 16374; (e) Zhu, S.-F.; Cai, Y.; Mao, H.-X.; Xie, J.-H.;
Zhou, Q.-L. Nat. Chem. 2010, 2, 546.
1
1
2. Gately, D. A.; Norton, J. R. J. Am. Chem. Soc. 1996, 118, 3479.
3. The product yields and enantioselectivities obtained with other solvents at
Acknowledgments
1
00 °C were as follows: o-xylene, 53% yield, 36% ee (R); chlorobenzene, 58%
yield, 29% ee (R); dimethylaniline, 23% yield, <1% ee; 1,4-dioxane, 56% yield,
20% ee (R); DMSO, 16% yield, 6% ee (R); aniline (neat), 21% yield, 12% ee (R).
4. Lower enantioselectivities by quinine- and quinidine-based catalysts are
consistent with our previous report in Ref. 4c
5. We also tested the NꢀH insertion reaction of two aliphatic amines,
benzylamine and cyclohexylamine, with phenyldiazoacetate 1b under similar
conditions. Unfortunately, the reaction was complex and the NꢀH insertion
products were not formed at all.
We thank Dr. Koichi Metori (Analytical Center, School of Phar-
macy, Nihon University) for performing the mass measurements.
We are grateful for financial support from the Research Institute
of Pharmacy, Nihon University.
1
1
Supplementary data
16. Tanzer, E.-M.; Schweizer, W. B.; Ebert, M.-O.; Gilmour, R. Chem. Eur. J. 2012, 18,
006.
2