K. P. Bryliakov and E. P. Talsi
and the mixture was allowed to cool down to room temperature. The
mixture was washed with water (240 mL) and dried over CaSO4. Vola-
tiles were removed and the desired complex was crystallized from
CH3CN/Et2O mixture. 1H spectra of complexes 1a and 1b synthesized ac-
cording to this procedure and according to the literature[8b] were identi-
cal.
K. Gorgy, J.-C. LeprÞtre, M.-N. Collomb, A. Deronzier, M. Fonte-
cave, S. Menage, Chem. Eur. J. 2002, 8, 1196–1204.
[6] a) J. Legros, C. Bolm, Angew. Chem. 2003, 115, 5645–5647; Angew.
Chem. Int. Ed. 2003, 42, 5487–5489; b) J. Legros, C. Bolm, Angew.
Chem. 2004, 116, 4321–4324; Angew. Chem. Int. Ed. 2004, 43, 4225–
4228; c) J. Legros, C. Bolm, Chem. Eur. J. 2005, 11, 1086–1092;
d) A. Korte, J. Legros, C. Bolm, C. Synlett. 2004, 13, 2397–2399.
[7] a) V.K. Sivasubramanian, M. Ganesan, S. Rajagopal, R. Ramaraj, J.
Org. Chem. 2002, 67, 1506–1514; b) K. P. Bryliakov, E. P. Talsi,
Angew. Chem. 2004, 116, 5340–5342; Angew. Chem. Int. Ed. 2004,
43, 5228–5230.
[8] a) W.-H. Leung, E. Y. Y. Chan, E. K. F. Chow, I. D. Williams, S.-M.
Peng, J. Chem. Soc. Dalton Trans. 1996, 1229–1236; b) T. Liu, Q.-X.
Liu, W.-H. Ruan, Z.-A. Zhu, Y.-T. Chen, A. S. C. Chan, Chin. J.
Chem. 2001, 19, 352–355; c) S. K. Edulji, S. T. Nguyen, Organome-
tallics 2003, 22, 3374–3381.
[9] a) A. X. Trautwein, E. Bill, E. L. Bominaar, H. Winkler, Struct.
Bonding 1998, 78, 1–95; b) K. Jayaraj, J. Terner, A. Gold, D. A.
Roberts, R. N. Austin, D. Mandon, R. Weiss, E. Bill, M. Muther,
A. X. Trautwein, Inorg. Chem. 1996, 35, 1632–1640; c) D. Mandon,
P. Ochsenbein, J. Fischer, R. Weiss, K. Jayaraj, R. N. Austin, A.
Gold, P. S. White, O. Brigaud, P. Battioni, D. Mansuy, Inorg. Chem.
1992, 31, 4404–4409; d) W. Nam, S. K. Choi, M. H. Lim, J.-U.
Rohde, I. Kim, J. Kim, C. Kim, L. Que, Angew. Chem. 2003, 115,
113–115; Angew. Chem. Int. Ed. 2003, 42, 109–111; e) W. J. Song,
Y. J. Sun, S. K. Choi, W. Nam, Chem. Eur. J. 2006, 12, 130–137.
[10] a) J. P. Collman, A. S. Chien, T. A. Eberspacher, J. I. Brauman, J.
Am. Chem. Soc. 2000, 122, 11098–11100; b) J. P. Collman, L. Zeng,
R. A. Decrꢂau, Chem. Commun. 2003, 2974–2975; c) Y. Yang, F.
Diederich, J. S. Valentine, J. Am. Chem. Soc. 1990, 112, 7826–7828;
d) S. H. Wang, B. S. Mandimutsira, R. Todd, B. Ramdhanie, J. P.
Fox, D. P. Goldberg, J. Am. Chem. Soc. 2004, 126, 18–19; J. P. Coll-
man, L. Zeng, J. I. Brauman, Inorg. Chem. 2004, 43, 2672–2679.
[11] 1H NMR spectroscopic monitoring of p-BrPhSMe oxidation with
PhIO catalyzed by 4 revealed that no decomposition of the dimeric
complex to monomers was observed at least after about 10 turn-
overs.
Complexes1b, 1h
: FeCl3 (0.55 mmol) was added to the ligand
(0.5 mmol) in MeOH (10 mL); the mixture was refluxed for 2 h and then
stirred at room temperature overnight. The solid formed was filtered off
and dried in vacuo.
Complexes1c, 1d, 1 f : FeCl3 (0.55 mmol) was added to the ligand
(0.5 mmol) in MeOH/CH2Cl2 mixture (1:1, 10 mL); the mixture was
stirred at room temperature for 8 h and then stored at À108Covernight.
The solid formed was filtered off and dried in vacuo.
Complexes1e, 1g, 2b : FeCl3 (0.55 mmol) was added to the ligand
(0.5 mmol) in MeOH/CH2Cl2 mixture (2:1, 10 mL); the mixture was re-
fluxed 2 h and stirred at room temperature for 8 h. The reaction mixture
was concentrated to 1 mL and the target product was purified by column
chromatography on SiO2 (eluent: hexane/ethyl acetate).
Complexes3a, 3b
: FeCl3 (0.50 mmol) was added to the ligand
(0.5 mmol) in MeOH/CH2Cl2 mixture (1:1, 10 mL); the mixture was re-
fluxed for 2 h, was concentrated to 5 mL at boiling temperature, and was
evaporated at room temperature in vacuo. The target products were sep-
arated on a column with SiO2 (eluent: hexane/ethyl acetate).
Complex 4: Water (1 drop) and Et2NH (0.2 mmol, 20 mL) were added to
a solution of complex 1a (0.2 mmol) in CH2Cl2 (3 mL) and the mixture
was stirred at room temperature overnight. The solution was washed
with water (5 mL) and dried over CaSO4, and volatiles were removed.
The residue was extracted with CH3CN, and the extract was diluted with
THF and Et2O, and allowed to evaporate slowly at room temperature to
give crystals of 4.
Acknowledgements
[12] a) H. Sasaki, R. Irie, T. Hamada, K. Suzuki, T. Katsuki, Tetrahedron
1994, 50, 11827–11838; b) K.-H. Ahn, S. W. Park, S. Choi, H.-J.
Kim, C. J. Moon, Tetrahedron Lett. 2001, 42, 2485–2488; c) B. Saito,
T. Katsuki, Tertrahedron Lett. 2001, 42, 3873–3876, and references
therein.
[13] a) K. P. Bryliakov, E. P. Talsi, J. Mol. Catal. A 2007, 264, 280–287;
b) A. Lattanzi, P. Iannece, A. Scretti, Tetrahedron: Asymmetry 2004,
15, 1779–1785; c) A. Lattanzi, P. Iannece, A. Scretti, Tetrahedron:
Asymmetry 2004, 15, 413–418; d) A. Massa, V. Mazza, A. Scretti,
Tetrahedron: Asymmetry 2005, 16, 2271–2275; e) H. B. Kagan, J. C.
Fiaud, Top. Stereochem. 1988, 18, 249–330.
[14] a) P. Piaggio, P. McMorn, D. Murphy, D. Bethell, P. C. Bulman Page,
F. E. Hankock, C. Sly, O. J. Kerton, G. I. Hutchings, J. Chem. Soc.
Perkin Trans. 2 2000, 2008–2015; b) U. H. Hirt, J. Org. Chem. 1998,
63, 7674; c) V. A. Nikiforov, V. S. Karavan, S. A. Miltsov, S. I. Seliva-
nov, E. Kolehmainen, E. Wegelius, M. Nissinen, ARKIVOC 2003,
VI, 191–200; d) C. Wilgerodt, Ber. Dtsch. Chem. Ges. 1892, 25,
3494–3502.
[15] a) M. Crawford, J. W. Rasburn, J. Chem. Soc. 1956, 2155–2160;
b) G. Casiraghi, G. Casnati, G. Puglia, G. Sartori, G. Terenghi, J.
Chem. Soc. Perkin Trans. 1 1980, 1862–1865.
The authors are grateful to the Russian Foundation for Basic Research,
grant 06-03-32214, for financial support.
[1] a) Catalytic Asymmetric Synthesis, 2nd ed. (Ed. I. Ojima) Wiley,
New York, 2000; b) Comprehensive Asymmetric Catalysis (Eds.:
E. N. Jacobsen, A. Pfaltz, H. Yamamoto), Springer, Berlin, 1999;
c) In 2006 the global sales of chiral drugs atorvastatine (LipitorTM
)
and (S)-omeprazole (NexiumTM) amounted to $11.7 billion (http://
com), respectively.
[2] a) J. Legros, J. R. Dehli, C. Bolm, Adv. Synth. Catal. 2005, 347, 19–
31; b) I. Fernandez, N. Khiar, Chem. Rev. 2003, 103, 3651–3706;
c) H.-J. Federsel, Chirality 2003, 15, S128-S142.
[3] a) P. Pitchen, H. B. Kagan, Tetrahedron Lett. 1984, 25, 1049–1052;
b) P. Pitchen, M. Desmukh, E. Dunach, H. B. Kagan, J. Am. Chem.
Soc. 1984, 106, 8188–8193; c) F. Di Furia, G. Modena, R. Seraglia,
Synthesis 1984, 325–326.
[4] C. Bolm, J. Legros, J. Le Paih, L. Zani, Chem. Rev. 2004, 104, 6217–
6254.
[5] a) J. T. Groves, P. J. Viski, J. Org. Chem. 1990, 55, 3628–3634; b) Y.
Naruta, F. Tani, K. Maruyama, J. Chem. Soc. Chem. Commun. 1990,
1378–1380; c) Y. Naruta, F. Tani, K. Maruyama, Tetrahedron: Asym-
metry 1991, 2, 533–542; d) L.-C. Chiang, K. Konishi, T. Aida, S.
Inoue, J. Chem. Soc. Chem. Commun. 1992, 254–256; e) Q. L.
Zhou, K. C. Chen, Z. H. Zhu, J. Mol. Catal. 1992, 72, 59–65; f) C .
Duboc-Toia, S. Menage, C. Lambeaux, M. Fontecave, Tetrahedron
Lett. 1997, 38, 3727–3730; g) C. Duboc-Toia, S. Menage, R. Y. Ho,
L. Que, Jr., C. Lambeaux, M. Fontecave, Inorg. Chem. 1999, 38,
1261–1268; h) Y. Mekmouche, H. Hummel, R. Y. N. Ho, L.
Que, Jr., V. Schünemann, F. Thomas, A. X. Trautwein, C. Lebrun,
[16] a) K. Srinivasan, P. Michaud, J. K. Kochi, J. Am. Chem. Soc. 1986,
108, 2309–2320; b) P. J. Pospisil, D. H. Carsten, E. N. Jacobsen,
Chem. Eur. J. 1996, 2, 974–980; c) J. F. Larrow, E. N. Jacobsen, Y.
Gao, Y. Hong, X. Nie, C. M. Zepp, J. Org. Chem. 1994, 59, 1939–
1942; d) M. Maneiro, M. R. Bermejo, M. I. Fernꢃndez, E. Gꢄmez-
Fꢄrneas, A. M. Gonzꢃlez-Noya, A. M. Tyryshkin, New J. Chem.
2003, 27, 727–733.
Received: April 12, 2007
Published online: July 4, 2007
8050
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Chem. Eur. J. 2007, 13, 8045 – 8050