LETTER
Conjugate Addition of 3-Substituted Oxindoles to Vinyl Sulfone
Scheidt, K. A. Angew. Chem. Int. Ed. 2007, 46, 8748.
1561
yields (80–95%) and excellent enantioselectivities (up to
99%) were observed for different substitution patterns on
the aryl group at C3. Both electron-withdrawing and elec-
tron-donating substrates on the C3 aryl group gave excel-
lent results.
(d) Trost, B. M.; Brennan, M. K. Synthesis 2009, 3003.
(2) For reviews, see: (a) Dounay, A. B.; Overman, L. E. Chem.
Rev. 2003, 103, 2945. (b) Galliford, C. V.; Scheidt, K. A.
Angew. Chem. Int. Ed. 2007, 46, 8748. (c) Lin, H.;
Danishefsky, S. J. Angew. Chem. Int. Ed. 2003, 42, 36.
(d) Rahman, A. U.; Basha, A. Indole Alkaloids; Harwood
Academic Publishers: Amsterdam, 1997. (e) Zhou, F.; Liu,
Y.-L.; Zhou, J. Adv. Synth. Catal. 2010, 352, 1381.
(3) (a) Mouri, S.; Chen, Z.; Mitsunuma, H.; Furutachi, M.;
Matsunaga, S.; Shibasaki, M. J. Am. Chem. Soc. 2010, 132,
1255. (b) Kato, Y.; Furutachi, M.; Chen, Z.; Mitsunuma, H.;
Matsunaga, S.; Shibasaki, M. J. Am. Chem. Soc. 2009, 131,
9168. (c) Tomita, D.; Yamatsugu, K.; Kanai, M.; Shibasaki,
M. J. Am. Chem. Soc. 2009, 131, 6946. (d) Linton, E. C.;
Kozlowski, M. C. J. Am. Chem. Soc. 2008, 130, 16162.
(e) Kundig, E. P.; Seidel, T. M.; Jia, Y.-X.; Bernardinelli, G.
Angew. Chem. Int. Ed. 2007, 46, 8484. (f) Shintani, R.;
Inoue, M.; Hayashi, T. Angew. Chem. Int. Ed. 2006, 45,
3353. (g) Dounay, A. B.; Hatanaka, K.; Kodanko, J. J.;
Oestreich, M.; Overman, L. E.; Pfeifer, L. A.; Weiss, M. M.
J. Am. Chem. Soc. 2003, 125, 6261. (h) Trost, B. M.;
Frederiksen, M. U. Angew. Chem. Int. Ed. 2005, 44, 308.
(i) Trost, B. M.; Zhang, Y. Chem. Eur. J. 2010, 16, 296.
(j) Trost, B. M.; Zhang, Y. J. Am. Chem. Soc. 2007, 129,
14548. (k) Hamashima, Y.; Suzuki, T.; Takano, H.;
Shimura, Y.; Sodeoka, M. J. Am. Chem. Soc. 2005, 127,
10164. (l) Corkey, B. K.; Toste, F. D. J. Am. Chem. Soc.
2007, 129, 2764. (m) Jia, Y.-X.; Hillgren, J. M.; Watson,
E. L.; Marsden, S. P.; Kundig, E. P. Chem. Commun. 2008,
4040. (n) Lee, S.; Hartwig, J. F. J. Org. Chem. 2001, 66,
3402. (o) Trost, B. M.; Czabaninuk, L. C. J. Am. Chem. Soc.
2010, 132, 15534.
Table 3 Variation of 3-Aryl-Substituted Oxindoles
Ar
R1
O
PhO2S
N
SO2Ph
Ar
Boc
R1
1
VIII (10 mol%)
+
O
CH2Cl2, 6 h, r.t.
N
SO2Ph
Boc
3
SO2Ph
2
Entry
1 Ar, R1
1f Ph, H
Yield (%)a
3f 90
ee (%)b
95
1
2
3
4
5
6
7
1g 3-MeC6H4, H
1h 4-MeC6H4, H
1i 3-MeOC6H4, H
1j 4-FC6H4, H
1k Ph, Me
3g 95
3h 80
3i 89
97
91
99
3j 91
93
3k 90
3l 92
95
1l Ph, F
85
(4) (a) Bui, T.; Syed, S.; Barbas, C. F. III. J. Am. Chem. Soc.
2009, 131, 8758. (b) Galzerano, P.; Bencivenni, G.;
Pesciaioli, F.; Mazzanti, A.; Giannichi, B.; Sambri, L.;
Bartoli, G.; Melchiorre, P. Chem. Eur. J. 2009, 15, 7846.
(c) Bravo, N.; Mon, I.; Companyo, X.; Alba, A.-N.; Moyano,
A.; Rios, R. Tetrahedron Lett. 2009, 50, 6624. (d) Li, X.;
Zhang, B.; Xi, Z.-G.; Luo, S.; Cheng, J.-P. Adv. Synth. Catal.
2010, 352, 416. (e) Li, X.; Xi, Z.-G.; Luo, S.; Cheng, J.-P.
Org. Biomol. Chem. 2010, 8, 77. (f) Pesciaioli, F.; Tian, X.;
Bencivenni, G.; Bartoli, G.; Melchiorre, P. Synlett 2010,
1704.
a Isolated yield.
b Enantiomeric excess of 3f–l was determined by HPLC analysis us-
ing Chiralcel OD-H (for 3f–j) and Chiralpak IB (for 3k–l) columns.
In conclusion, we have developed a highly efficient cata-
lytic enantioselective conjugate addition reactions of both
3-alkyl- and 3-aryl-substituted oxindoles 1a–l to 1,1-
bis(benzenesulfonyl)ethylene (2) using binaphthyl-modi-
fied bifunctional catalysts V and VIII. The desired
Michael products were obtained in good to high yields,
and excellent enantioselectivities (up to 99% ee) were ob-
served for all the substrates examined in this work. We be-
lieve that this method provides a practical entry for the
preparation of synthesis of medicinally useful chiral 3,3-
disubstituted oxindoles. Further study of these bifunction-
al organocatalysts in other asymmetric reactions is under
investigation.
(5) For reviews, see: (a) Simpkins, N. S. Tetrahedron 1990, 46,
6951. (b) Najera, C.; Yus, M. Tetrahedron 1999, 55, 10547.
(c) Nielsen, M.; Jacobsen, C. B.; Holub, N.; Paixao, M. W.;
Jørgensen, K. A. Angew. Chem. Int. Ed. 2010, 49, 2668.
(d) Zhu, Q.; Lu, Y. Aust. J. Chem. 2009, 62, 95. (e) Alba,
A.-N. R.; Companya, X.; Rios, R. Chem. Soc. Rev. 2010, 39,
2018.
(6) (a) Zhu, Q.; Lu, Y. Org. Lett. 2008, 10, 4803. (b) Zhu, Q.;
Cheng, L.; Lu, Y. Chem. Commun. 2008, 6315. (c) Zhu, Q.;
Lu, Y. Org. Lett. 2009, 11, 1721. (d) Zhu, Q.; Lu, Y. Chem.
Commun. 2010, 46, 2235. (e) Li, H.; Song, J.; Liu, X.; Deng,
L. J. Am. Chem. Soc. 2005, 127, 8948. (f) Li, H.; Song, J.;
Deng, L. Tetrahedron 2009, 65, 3139. (g) Moss, S.;
Alexakis, A. Org. Lett. 2005, 7, 4361. (h) Quintard, A.;
Bournaud, C.; Alexakis, A. Chem. Eur. J. 2008, 14, 7504.
(i) Quintard, A.; Alexakis, A. Chem. Eur. J. 2009, 15,
11109. (j) Sulzer-Moss, S.; Alexakis, A.; Mareda, J.; Bollot,
G.; Bernardinelli, G.; Filinchuk, Y. Chem. Eur. J. 2009, 15,
3204. (k) Quintard, A.; Belot, S.; Sebastien, M.; Marchal, E.;
Alexakis, A. Eur. J. Org. Chem. 2010, 927. (l) Quintard,
A.; Alexakis, A. Chem. Commun. 2010, 46, 4085.
Acknowledgement
This research was supported by Basic Science Research Program
through the National Research Foundation of Korea (NRF) founded
by the Ministry of Education, Science and Technology (2010-
0002488).
References and Notes
(1) For selected reviews, see: (a) Marti, C.; Carreira, E. M. Eur.
J. Org. Chem. 2003, 2209. (b) Dounay, A. B.; Overman,
L. E. Chem. Rev. 2003, 103, 2945. (c) Galliford, C. V.;
(m) Landa, A.; Maestro, M.; Masdeu, C.; Puente, A.; Vera,
Synlett 2011, No. 11, 1559–1562 © Thieme Stuttgart · New York