1800
R. Millet, A. Alexakis
LETTER
(9) Marino, J. P.; Floyd, D. M. Tetrahedron Lett. 1979, 25, 675.
(10) Bertozzi, F.; Crotti, P.; Macchia, F.; Pineschi, M.; Feringa,
B. L. Angew. Chem. Int. Ed. 2001, 40, 930.
References and Notes
(1) Modern Organocopper Chemistry; Krause, N., Ed.; Wiley-
VCH: Weinheim, 2002.
(2) Vedjes, E.; Jure, M. Angew. Chem. Int. Ed. 2005, 44, 3974;
and references cited therein.
(3) (a) Badalassi, F.; Crotti, P.; Macchia, F.; Pineschi, M.;
Arnold, A.; Feringa, B. L. Tetrahedron Lett. 1998, 39, 7795.
(b) For a review, see: Pineschi, M. New J. Chem. 2004, 28,
657; and references cited therein.
(4) Equey, O.; Alexakis, A. Tetrahedron: Asymmetry 2004, 15,
1531.
(5) Millet, R.; Alexakis, A. Synlett 2007, 435.
(6) Palais, L.; Mikhel, I. S.; Bournaud, C.; Micouin, L.; Falciola,
C. A.; Vuagnoux-d’Augustin, M.; Rosset, S.; Bernardinelli,
G.; Alexakis, A. Angew. Chem. Int. Ed. 2007, 46, 7462.
(7) (a) Yorimitsu, H.; Oshima, K. Angew. Chem. Int. Ed. 2005,
44, 4435. (b) Alexakis, A.; Malan, C.; Lea, L.; Tissot-
Croset, K.; Polet, D.; Falciola, C. Chimia 2006, 60, 124.
(c) Tissot-Croset, K.; Polet, D.; Alexakis, A. Angew. Chem.
Int. Ed. 2004, 43, 2426. (d) Alexakis, A.; Croset, K. Org.
Lett. 2002, 4, 4147. (e) For a very recent review, see:
Falciola, C. A.; Alexakis, A. Eur. J. Org. Chem. 2008, DOI:
10.1002/ejoc.200800025.
(11) Typical Procedure
In a dried Schlenk tube under N2 atmosphere were placed
CuTC (5.7 mg, 0.03 mmol) and (S,S)-L1 (13.5 mg, 0.03
mmol). Then, CH2Cl2 was added (6 mL) and the mixture was
stirred at r.t. for 20 min. The tube was cooled down to –78 °C
and 1,3-cyclohexadiene monoepoxide 1 (100 mL, 1 mmol)
was added. c-HexMgCl (250 mL, 2.0 M in Et2O, 0.5 mmol)
was added dropwise over a period of 3 min. The reaction was
stirred for 3 h and quenched with MeOH and (NH4)2SO4
before being allowed to reach r.t. The aqueous phase was
extracted with CH2Cl2 and the organic layer was dried over
MgSO4 and the solvent removed on rotary evaporator (55%
conversion, 88% ee). The crude product was purified by
flash chromatography on SiO2 (pentane then pentane–Et2O,
20
75:25) yielding 79 mg (44% yield) of a white solid. [a]D
–128.2 (c 0.87, CHCl3, ee = 88%). 1H NMR (400 MHz,
CDCl3): d = 5.68 (m, 2 H), 4.20 (br, 1 H), 2.09 (m, 1 H), 1.97
(m, 1 H), 1.74–1.60 (m, 6 H), 1.45–1.35 (m, 3 H), 1.22–1.12
(m, 4 H), 1.07–0.97 (m, 2 H). 13C NMR (100 MHz, CDCl3):
d = 133.3, 130.1, 67.5, 42.4, 41.1, 32.7, 30.2, 29.7, 26.7,
23.7.
(8) Alexakis, A.; Benhaim, C.; Rosset, S.; Humam, M. J. Am.
Chem. Soc. 2002, 124, 5262.
Synlett 2008, No. 12, 1797–1800 © Thieme Stuttgart · New York