LETTER
Synthesis of Chiral Calixarene-Like Salen Ligand
1223
Rajagopal, S.; Srinivasan, C.; Alhaji, N. I.; Chellamani, A. J.
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3, 3053.
Table 2 Enantioselective Friedel–Crafts Reaction of Aromatic
Amines with Glyoxylate Catalyzed by Ti-6 Complexa
O
OH
+
ArH
H
CO2R
Ar
*
CO2R
(4) (a) Zhang, H. C.; Huang, W. S.; Pu, L. J. Org. Chem. 2001,
66, 481. (b) Gao, J.; Reibenspies, J. H.; Martell, A. E.
Angew. Chem. Int. Ed. 2003, 42, 600. (c) Li, Z. M.;
Jablonski, C. Inorg. Chem. 2000, 39, 2456.
Entry Amine
Glyoxylate
Yield (%)b OR/ee (%)c
1
85
(S)d-(+) 98
O
NMe2
(5) (a) Bohmer, V. Angew. Chem., Int. Ed. Engl. 1995, 34, 713.
(b) Casnati, A.; Sansone, F.; Ungaro, R. Acc. Chem. Res.
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2005, 7, 1927. (e) Huang, Y. J.; Yang, F. Y.; Zhu, C. J. J.
Am. Chem. Soc. 2005, 127, 16386.
H
CO2Et
2
90
78
(+) 57
(+) 84
O
O
NMe2
H
H
CO2Me
CO2Et
3
NMe2
H3C
H3C
4
80
(+) 76
NMe2
O
(7) No, K.; Kwon, K. Y. Synthesis 1996, 1293.
(8) Cox, P. J.; Wang, W.; Snieckus, V. Tetrahedron Lett. 1992,
33, 2253.
H
CO2Me
(9) Procedure for the Synthesis of Compound 6.
To a solution of 1.5 g (2.80 mmol) diformyl triphenol (5) in
100 mL of dry CH2Cl2 was added 0.34 g (3 mmol) (1R,2R)-
1,2-diaminocyclohexane and 2 g anhyd Na2SO4. The
mixture was stirred for 24 h at r.t. After the solids were
filtered, the solution was reduced to about 10 mL in vacuo.
Addition of 30 mL of MeOH gave a yellow solid, which was
then recrystallized with CH2Cl2–MeOH (1:1) to give 1.1 g of
compound 6 (yield: 65%), yellow solid, mp 130–132 °C,
[a]D25 –25.8 (c 0.6, CH2Cl2). 1H NMR (300 MHz, CDCl3):
d = 14.05 (s, 3 H), 8.22 (s, 2 H), 7.07 (s, 2 H), 7.04 (s, 2 H),
6.97 (s, 2 H), 4.09 (d, J = 14.2 Hz, 2 H), 3.84 (d, J = 14.2 Hz,
2 H), 3.32 (s, 4 H), 1.91–1.40 (m, 8 H), 1.21 (s, 18 H), 1.19
(s, 9 H) ppm. 13C NMR (300 MHz, CDCl3): d = 165.7, 158.5,
141.0, 131.7, 129.1, 127.4, 126.4, 125.9, 117.2, 72.0, 34.2,
33.6, 31.9, 31.7, 31.2, 24.5 ppm. IR (KBr): n = 3421, 3252,
2935, 2890, 1628, 1532, 1485, 1410, 1360 cm–1. MS (ES):
m/z (%) = 609.5 (100). Anal. Calcd (%) for C40H52N2O3: C,
78.95; H, 8.55; N, 4.62. Found: C, 78.92; H, 8.60; N, 4.50.
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A. Angew. Chem. Int. Ed. 2001, 40, 160. (b) Zhou, J.; Tang,
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MacMillan, D. W. J. Am. Chem. Soc. 2002, 124, 7894.
(d) Evans, D. A.; Scheidt, K. S.; Fandrick, K. R.; Lam, H. J.;
Wu, J. J. Am. Chem. Soc. 2003, 125, 10780. (e) Ishii, A.;
Soloshonok, V. A.; Mikami, K. J. Org. Chem. 2000, 65,
1597.
5
6
81
84
(+) 50
(+) 93
O
O
NMe2
NMe2
H
H
CO2Et
CO2Me
a Reaction conditions: aromatic amine (1.0 mmol), glyoxylate (2.0
mmol), catalyst (5 mol%), Et2O (2 mL), 0 °C, 20–24 h.
b Isolated yield by prepared TLC.
c Determined by HPLC analysis on a Chiralcel OD-H chiral column.
d The absolute configuration was determined by comparing the opti-
cal rotation with the literature value.14
catalyst, and provide modest to excellent enantioselectiv-
ities. Further studies on the structure of the catalyst and
the application of this new ligand on other asymmetric re-
actions are now in progress in our laboratory.
Acknowledgment
We gratefully acknowledge the National Natural Science Foundati-
on of China (20472028, 20332050) and Education Ministry for their
financial support.
(11) (a) Gathergood, N.; Zhuang, W.; Jørgensen, K. A. J. Am.
Chem. Soc. 2000, 122, 12517. (b) Yuan, Y.; Wang, X. W.;
Li, X.; Ding, K. L. J. Org. Chem. 2004, 69, 146.
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Matsuo, M. Chem. Pharm. Bull. 1993, 41, 2050.
(b) Khalaj, A.; Shadnia, H.; Sharifzadeh, M. Pharm.
Pharmacol. Commun. 1998, 4, 373. (c) Miersch, O.;
Kramell, R.; Parthier, B.; Wasternack, C. Phytochemistry
1999, 50, 353.
References and Notes
(1) For reviews, see: Chem. Rev. 2003, 103, 2761-3400
(thematic issue of enantioselective catalysis).
(2) (a) Jacobsen, E. N.; Zhang, W.; Muci, A. R.; Ecker, J. R.;
Deng, L. J. Am. Chem. Soc. 1991, 113, 7063. (b) Bennani,
Y. L.; Hanessian, S. Chem. Rev. 1997, 97, 3161. (c) Canali,
L.; Sherrington, D. C. Chem. Soc. Rev. 1999, 28, 85.
(3) (a) Mcgarrigle, E. M.; Murphy, D. M.; Gilheany, D. G.
Tetrahedron: Asymmetry 2004, 15, 1343. (b) Liu, X. W.;
Tang, N.; Chang, Y. H.; Tan, M. Y. Tetrahedron:
(13) Typical Procedure for the Asymmetric Friedel–Crafts
Reaction of Aromatic Amine with Glyoxylate.
In a 15-mL Schlenk tube, salen compound 6 (32 mg, 0.05
mmol) was dissolved in 2 mL of Et2O under argon
atmosphere, followed by the addition of titanium
tetraisopropoxide (0.5 M in Et2O, 100 mL, 0.05 mmol) and
the mixture was stirred for 2 h at r.t. The resulting solution
Asymmetry 2004, 15, 1269. (c) Bryliakov, K. P.; Talsi, E. P.
Angew. Chem. Int. Ed. 2004, 43, 5228. (d) Sevvel, R.;
Synlett 2006, No. 8, 1221–1224 © Thieme Stuttgart · New York