DOI: 10.1039/C4CC04235B
Page 3 of 3
Journal Name
ChemComm
COMMUNICATION
aliphatic substituent (R1 = n-Bu) was also tolerated, thus affording 3hd
in 94% yield and 88% ee.
J. R. Heemstra and G. L. Beutner, Angew. Chem. Int. Ed., 2005, 44,
4682-4698; (c) G. Casiraghi, L. Battistini, C. Curti, G. Rassu and F.
Zanardi, Chem. Rev., 2011, 111, 3076-3154; (d) S. V. Pansare and E.
K. Paul, Chem.-Eur. J., 2011, 17, 8770-8779; (d) V. Bisai, Synthesis,
2012, 1453-1463.
Table 3. Substrate scope of the enantioselective vinylogous aldol/cyclization
cascade reactiona
2. For review, see: (a) Q. Zhang, X. Liu and X. Feng, Curr. Org. Synth.,
2013, 10, 764-785. For other examples, see: (b) K. Das Sarma, J.
Zhang and T. T. Curran, J. Org. Chem., 2007, 72, 3311-3318; (c) H.
Ube, N. Shimada and M. Terada, Angew. Chem. Int. Ed., 2010, 49,
1858-1861; (d) Y. Yang, K. Zheng, J. Zhao, J. Shi, L. Lin, X. Liu and
X. Feng, J. Org. Chem., 2010, 75, 5382-5384; (e) J. Luo, H. Wang, X.
Han, L.-W. Xu, J. Kwiatkowski, K.-W. Huang and Y. Lu, Angew.
Chem. Int. Ed., 2011, 50, 1861-1864; (f) S. V. Pansare and E. K. Paul,
Chem. Commun., 2011, 47, 1027-1029; (g) A. Claraz, S. Oudeyer and
V. Levacher, Adv. Synth. Catal., 2013, 355, 841-846.
Entry
1
2
3
4
5
6
7
8
R2, R3
H, Me
H, Bn
H, Boc
H, H
R1
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Time (h) Yield (%)b Ee (%)c
16
16
48
18
12
12
24
20
12
12
12
12
12
48
12
8
3aa, 99
3ab, 98
3ac, trace
3ad, 98
3ae, 98
3af, 98
3ag, 98
3ah, 97
3ai, 99
91
91
n.d
94
88
84
97
92
90
86
86
92
92
94
88
85
82
95
93
92
92
93
95
88
4-Cl, H
4-Br, H
5-Me, H
5-MeO, H
5-F, H
5-Cl, H
5-Br, H
6-Cl, H
6-Br, H
7-Me, H
7-F, H
7-Cl, H
7-Br, H
H, H
H, H
H, H
H, H
H, H
H, H
H, H
3. (a) D. Bastida, Y. Liu, X. Tian, E. Escudero-Adán and P. Melchiorre,
Org. Lett., 2012, 15, 220-223; (b) C. Cassani and P. Melchiorre, Org.
Lett., 2012, 14, 5590-5593.
4. (a) R. Yazaki, N. Kumagai and M. Shibasaki, J. Am. Chem. Soc.,
2010, 132, 5522-5531; (b) Y. Otsuka, H. Takada, S. Yasuda, N.
Kumagai and M. Shibasaki, Chem.-Asian J., 2013, 8, 354-358; (c) A.
Saito, N. Kumagai and M. Shibasaki, Tetrahedron Lett., 2014, 55,
3167-3171..
9
10
11
12
13
14
15
16
16
18
19
20
21
22
23
24
3aj, 98
3ak, 98
3al, 99
3am, 97
3an, 98
3ao, 98
3ap, 99
3aq, 99
3bd, 98
3cd, 99
3dd, 99
3ed, 93
3fd, 97
3gd, 98
3hd, 94
5. B. Zhu, W. Zhang, R. Lee, Z. Han, W. Yang, D. Tan, K.-W. Huang
and Z. Jiang, Angew. Chem. Int. Ed., 2013, 52, 6666-6670.
6. B. Tan, G. Hernández-Torres and C. F. Barbas III, Angew. Chem. Int.
Ed., 2012, 51, 5381-5385.
Ph
8
4-CF3C6H4
4-ClC6H4
4-FC6H4
4-OMeC6H4
4-MeC6H4
3-MeC6H4
n-C4H9
18
18
18
36
36
24
24
7. T.-Z. Li, X.-B. Wang, F. Sha and X.-Y. Wu, J. Org. Chem., 2014, 79,
4332-4339.
8. For review, see: D. Cheng, Y. Ishihara, B. Tan and C. F. Barbas III,
ACS Catal., 2014, 4, 743-762.
a The reactions were carried out with isatins (0.2 mmol), allyl pyrazoleamides
(0.3 mmol) and A5 (0.002 mol) in 2 mL CH3CN at 25 °C. b Isolated yields. c
The ee values were determined by chiral HPLC analysis.
9. (a) D. Hojo, K. Noguchi, M. Hirano and K. Tanaka, Angew. Chem.
Int. Ed., 2008, 47, 5820-5822. (b) L.-T. Shen, P.-L. Shao and S. Ye,
Adv. Synth. Catal., 2011, 353, 1943-1948; (c) C. Yao, Z. Xiao, R. Liu,
T. Li, W. Jiao and C. Yu, Chem.-Eur. J., 2013, 19, 456-459; (d) R.
Liu, C. Yu, Z. Xiao, T. Li, X. Wang, Y. Xie and C. Yao, Org. Biomol.
Chem., 2014, 12, 1885-1891.
In conclusion, we have developed the first enaotioselective
vinylogous aldol/cyclization cascade reaction between allyl
pyrazoleamides and isatins. Excellent yields (93-99%) and good-to-
10. (a) C.-C. Wang and X.-Y. Wu, Tetrahedron, 2011, 67, 2974-2978; (b)
J.-Y. Qian, C.-C. Wang, F. Sha and X.-Y. Wu, RSC Adv., 2012, 2,
6042-6048; (c) T.-Z. Li, X.-B. Wang, F. Sha and X.-Y. Wu,
Tetrahedron, 2013, 69, 7314-7319; (d) X.-B. Wang, T.-Z. Li, F. Sha
and X.-Y. Wu, Eur. J. Org. Chem., 2014, 739-744.
excellent enantioselectivities (82-97
presence of only 1 mol% of Takemoto catalyst A5. This methodology
establishes new protocol for the asymmetric construction of
% ee) were achieved in the
a
structurally novel spirocyclic oxindole-dihydropyranones.
We are grateful for the financial support from National Natural
Science Foundation of China (21242007, 21102043) and the
Fundamental Research Funds for the Central Universities.
11. T. Okino, Y. Hoashi and Y. Takemoto, J. Am. Chem. Soc., 2003, 125,
12672-12673.
Notes and references
Key Laboratory for Advanced Materials and Institute of Fine Chemicals,
East China University of Science and Technology, 130 Meilong Road,
Shanghai 200237, P. R. China, Tel: +86-21-64252011, Email:
Electronic Supplementary Information (ESI) available: [Experimental
procedures, structural proofs, NMR spectra and HPLC chromatograms of
the products]. See DOI: 10.1039/c000000x/
1. For selected reviews, see: (a) G. Casiraghi, F. Zanardi, G. Appendino
and G. Rassu, Chem. Rev., 2000, 100, 1929-1972; (b) S. E. Denmark,
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 3