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T. Okamatsu et al.
LETTER
(10) For the representative related studies on the helical chirality
induced by tripodal tertiary amine ligands, see: (a) Canary,
J. W.; Allen, C. S.; Castagnetto, J. M.; Wang, Y. J. Am.
Chem. Soc. 1995, 117, 8484. (b) Dai, Z.; Xu, X.; Canary, J.
W. Chirality 2005, 17, S227.
(11) The identical architecture was also reported for achiral N,N-
bis(2-hydroxybenzyl)-2-picolylamine: Vencato, I.; Neves,
A.; Ceccato, A. S.; Horn, A. Jr. Acta Crystallogr., Sect. C
1996, 52, 949.
References and Notes
(1) Current address: Department of Chemistry, Graduate School
of Science and Technology, Kumamoto University, 2-39-1
Kurokami, Kumamoto 860-8555, Japan. E-mail:
(2) (a) Dalco, P. I.; Moisan, L. Angew. Chem. Int. Ed. 2001, 40,
3726. (b) Jarvo, E. R.; Miller, S. J. Tetrahedron 2002, 58,
2481. (c) Dalco, P. I.; Moisan, L. Angew. Chem. Int. Ed.
2004, 43, 5138. (d) Berkessel, A.; Grögger, H. Asymmetric
Organocatalysis; Wiley-VCH: Weinheim, 2005.
(e) France, S.; Guerin, D. J.; Miller, S. J.; Lectka, T. Chem.
Rev. 2003, 103, 2985.
(12) (a) Marcelli, T.; van Maarseveen, J. H.; Hiemstra, H. Angew.
Chem. Int. Ed. 2006, 45, 7496. (b) Akiyama, T.; Itoh, J.;
Fuchibe, K. Adv. Synth. Catal. 2006, 348, 999.
(13) Although we used the (R,R)-isomer of 1 in our previous
report (ref. 8), this work was performed with (S,S)-1.
(14) Typical Procedure for Catalytic Asymmetric Methanolysis
of Cyclic meso-Anhydrides: To a solution or suspension
of cyclic meso-anhydride (0.1 mmol) and 1 (1.8 mg, 5 mmol)
in dist. toluene (1–2.5 mL) was added MeOH (20–81 mL,
0.5–2.0 mmol) at the temperature specified in Table 1 and
Table 2. After being stirred at the temperature for 24 h, an
aliquot of the reaction mixture was concentrated and
subjected to 1H NMR analysis. The chemical yield was
estimated from the ratio of the unreacted anhydride and the
hemiester produced, which were the only two components in
the crude reaction mixture. Then, whole the mixture was
acidified with aq HCl (1 M, 1.0 mL) to extract 1 into the
aqueous phase. The phases were separated and the product in
the organic layer was extracted with sat. NaHCO3 (2 × 1.0
mL), leaving the starting material in the organic layer. After
the organic layer was discarded, the aqueous layer was
acidified with aq HCl (1 M, 2.0 mL) and extracted with
EtOAc (3 × 2.0 mL). The combined organic layer was dried
over Na2SO4 and concentrated in vacuo to give the desired
hemiester in almost pure form judged by the 1H NMR
analysis.
(15) The conditions for the HPLC analysis of each compound are
as follows: 3a: DAICEL CHIRALCELL AS-H, hexane–2-
propanol–CF3COOH = 95:5:0.1, 0.3 mL/min. Carboxanilide
of 3b: DAICEL CHIRALCELL AD-H, hexane–2-pro-
panol = 90:10, 0.5 mL/min. Carboxanilide of 3c: DAICEL
CHIRALCELL OD-H, hexane–2-propanol = 90:10, 0.5 mL/
min. p-Bromophenyl ester of 3d: DAICEL CHIRALCELL
OD-H, hexane–2-propanol = 98:2, 0.5 mL/min. p-Bromo-
phenyl ester of 3e: DAICEL CHIRALCELL OD-H, hexane–
2-propanol = 98:2, 0.5 mL/min. Carboxanilide of 3f:
DAICEL CHIRALCELL OD-H, hexane–2-propanol = 92:8,
0.5 mL/min. 3g: DAICEL CHIRALCELL AD-H, hexane–2-
propanol–CF3COOH = 90:10:0.1, 0.5 mL/min.
(3) Chen, Y.; McDaid, P.; Deng, L. Chem. Rev. 2003, 103, 2965.
(4) (a) Hiratake, J.; Yamamoto, Y.; Oda, J. J. Chem. Soc., Chem.
Commun. 1985, 1717. (b) Hiratake, J.; Inagaki, M.;
Yamamoto, Y.; Oda, J. J. Chem. Soc., Perkin Trans. 1 1987,
1053. (c) Aitken, R. A.; Gopal, J.; Hirst, J. A. J. Chem. Soc.,
Chem. Commun. 1988, 632. (d) Bolm, C.; Gerlach, A.;
Dinter, C. L. Synlett 1999, 195. (e) Bolm, C.; Schiffers, I.;
Dinter, C. L.; Gerlach, A. J. Org. Chem. 2000, 65, 6984.
(f) Chen, Y.; Tian, S.-K.; Deng, L. J. Am. Chem. Soc. 2000,
122, 9542. (g) Bolm, C.; Schiffers, I.; Atodiresei, I.;
Hackenberger, C. P. R. Tetrahedron: Asymmetry 2003, 14,
3455. (h) Rodriguez, B.; Rantanen, T.; Bolm, C. Angew.
Chem. Int. Ed. 2006, 45, 6924.
(5) Bolm et al. also devised a catalytic system with a
stoichiometric amount of sacrificial achiral amine.4e
(6) Uozumi, Y.; Yasoshima, K.; Miyachi, T.; Nagai, S.-I.
Tetrahedron Lett. 2001, 42, 411.
(7) Honjo, T.; Sano, S.; Shiro, M.; Nagao, Y. Angew. Chem. Int.
Ed. 2005, 44, 5838.
(8) Various transition-metal-catalyzed asymmetric ring-
opening reactions of cyclic meso-anhydrides were also
reported: (a) Seebach, D.; Jaeschke, G.; Wang, Y. M.
Angew. Chem., Int. Ed. Engl. 1995, 34, 2395. (b) Shintani,
R.; Fu, G. C. Angew. Chem. Int. Ed. 2002, 41, 1057.
(c) Bercot, E. A.; Rovis, T. J. Am. Chem. Soc. 2002, 124,
174. (d) Bercot, E. A.; Rovis, T. J. Am. Chem. Soc. 2004,
126, 10248. For the related asymmetric desymmetrization
of cyclic meso-anhydrides with stoichiometric chiral
alcohols and amines, see: (e) Ohshima, M.; Mukaiyama, T.
Chem. Lett. 1987, 377. (f) Ohtani, M.; Matsuura, T.;
Watanabe, F.; Narisada, M. J. Org. Chem. 1991, 56, 4120.
(g) Theisen, P. D.; Heathcock, C. H. J. Org. Chem. 1993, 58,
142. (h) Hashimoto, N.; Kawamura, S.; Ishizuka, T.;
Kunieda, T. Tetrahedron Lett. 1996, 37, 9237. (i) Jones, I.
G.; Jones, W.; North, M.; Teijeira, M.; Uriarte, E.
Tetrahedron Lett. 1997, 38, 889. (j) Hibbs, D. E.;
Hursthouse, M. B.; Jones, I. G.; Jones, W.; Malic, K. M. A.;
North, M. J. Org. Chem. 1999, 64, 5413. (k) Evans, A. C.;
Longbottom, D. A.; Matsuoka, M.; Ley, S. V. Synlett 2005,
646.
Carboxanilide of 3h: DAICEL CHIRALCELL AS-H,
hexane–2-propanol = 70:30, 0.5 mL/min. Carboxanilide of
3i: DAICEL CHIRALCELL OJ-H, hexane–2-propanol =
90:10, 0.5 mL/min.
(16) Mori, K.; Tomioka, H.; Fukuyo, E.; Yanagi, K. Liebigs Ann.
Chem. 1993, 671.
(9) Okamatsu, T.; Irie, R.; Katsuki, T. J. Organomet. Chem.
2007, 692, 645.
(17) Bigi, F.; Carloni, S.; Maggi, R.; Mazzacani, A.; Sartori, G.;
Tanzi, G. J. Mol. Catal. A: Chem. 2002, 182-183, 533.
(18) The authors are grateful to a reviewer for useful suggestions
about the mechanism of this reaction that is now under
investigation in our laboratory.
Synlett 2007, No. 10, 1569–1572 © Thieme Stuttgart · New York