LETTER
Addition of Organometallic Reagents to a Chiral C2-Symmetrical Bisimine
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(3) (a) Roland, S.; Mangeney, P.; Alexakis, A. Synthesis 1999,
228. (b) Roland, S.; Mangeney, P. Eur. J. Org. Chem. 2000,
611. (c) Alvaro, G.; Grepioni, F.; Savoia, D. J. Org. Chem.
1997, 62, 4180. (d) Alvaro, G.; Grepioni, F.; Grilli, S.;
Maini, L.; Martelli, G.; Savoia, D. Synthesis 2000, 581.
(4) (a) Alexakis, A.; Tomassini, A.; Chouillet, C.; Roland, S.;
Mangeney, P.; Bernardinelli, G. Angew. Chem. Int. Ed.
2000, 39, 4093. (b) Grilli, S.; Martelli, G.; Savoia, D.;
Zazzetta, C. Synthesis 2003, 1083.
(5) For recent leading references, see: (a) Enders, D.; Meiers,
M. Angew. Chem., Int. Ed. Engl. 1996, 35, 2261.
(b) Prakash, G. K. S.; Mandal, M. J. Am. Chem. Soc. 2002,
124, 6538. (c) Zhong, Y. W.; Xu, M. H.; Lin, G. Q. Org.
Lett. 2004, 6, 3953. (d) Zhong, Y. W.; Izumi, K.; Xu, M. H.;
Lin, G. Q. Org. Lett. 2004, 6, 4747. (e) Xue, D.; Chen, Y.;
Cui, X.; Wang, Q.; Zhu, J.; Deng, J. J. Org. Chem. 2005, 70,
3584.
(6) Liao, J.; Sun, X.; Cui, X.; Yu, K.; Zhu, J.; Deng, J. Chem.
Eur. J. 2003, 9, 2611.
(7) (a) Liu, G.; Cogan, D. A.; Ellman, J. A. J. Am. Chem. Soc.
1997, 119, 9913. (b) Liu, G.; Cogan, D. A.; Owens, T. D.;
Tang, T. P.; Ellman, J. A. J. Org. Chem. 1999, 64, 1278.
(8) Procedure for the Synthesis of Bisimine 2.
To a 0.25 M solution of (R)-tert-butanesulfinamide (1, 1.21
g, 10 mmol) in CH2Cl2 (40 mL) was added 6.4 g (40 mmol)
of anhyd CuSO4 followed by 40% aq glyoxal (0.72 mL, 5
mmol). The mixture was stirred at r.t. for 2 d. The reaction
mixture was filtered through a pad of Celite, and the filter
cake was washed well with CH2Cl2. The residue obtained
after condensation was purified by chromatography twice.
Pure 2 was obtained (0.94 g, 71%) as a pale yellow
crystalline solid after recrystallized twice from hexane.
(9) For addition reactions to sulfinimines, see: (a) Ellman, J.
A.; Owens, T. D.; Tang, T. P. Acc. Chem. Res. 2002, 35, 984;
and references therein. (b) Evans, J. W.; Ellman, J. A. J.
Org. Chem. 2003, 68, 9948. (c) McMahon, J. P.; Ellman, J.
A. Org. Lett. 2004, 6, 1645. (d) Schenkel, L. B.; Ellman, J.
A. Org. Lett. 2004, 6, 3621.
Figure 1 X-ray crystal structure of (R,R)-3e
O
S
R
O
S
H
from Re face
from Re face
H
H
RLi
RLi
N
N
Li
O
O
N
N
F3B
F3B
BF3
BF3
A
B
Figure 2 The mechanism for organolithium addition to bisimine 2
(10) Cogan, D. A.; Liu, G.; Ellman, J. A. Tetrahedron 1999, 55,
8883; and references therein.
To a flask was added the bisimine (R,R)-2 in the specified solvent
and the solution was then cooled to –78 °C under Ar. The organo-
metallic reagent (4 equiv) was then added slowly to the solution and
then stirred for 3–5 h. The reaction mixture was allowed to warm to
r.t. over a period of 5 h and then stirred for a further 2 h. The mixture
was cooled to 0 °C and quenched by the addition of a sat. aq solu-
tion of Na2SO4. The organic phase was separated and the aqueous
phase was extracted with EtOAc. The combined organic layers
were dried over MgSO4, filtered and concentrated. The residue was
purified via flash chromatography to afford the disulfinamide 3.
(11) Davis, F. A.; McCoull, W. J. Org. Chem. 1999, 64, 3396.
(12) For Barbier allylation of chiral imines, see: (a) Legros, J.;
Meyer, F.; Coliboeuf, M.; Crousse, B.; Bonnet-Delpon, D.;
Bégué, J.-P. J. Org. Chem. 2003, 68, 6444. (b) Lee, C.-L.
K.; Ling, H. Y.; Loh, T.-P. J. Org. Chem. 2004, 69, 7787.
(13) X-ray Investigation and Crystal Data.
Colorless crystals of (R,R)-3e were grown from Et2O at r.t.
The X-ray diffraction data were collected on a Siemens P4
automatic four-circle diffractometer using graphite
monochromated Mo-Ka radiation (l = 0.71073 Å) at r.t. The
structure was solved by direct methods using SHELXS-97
and refined by full-matrix least-square calculation on F2
with SHELXL-97. Crystal data for (R,R)-3e
Acknowledgment
We thank the financial support by the National Natural Science
Foundation of China (No. 20025205, 203900507 and 20372061).
(C24H38N2O3S2): Mw = 466.68, crystal size
0.48 × 0.44 × 0.42 mm, orthorhombic, space group P2 (1)2
(1)2 (1), a = 7.100 (1) Å, b = 19.026 (2) Å, c = 20.197 (2)
Å, a = 90°, b = 90°, g = 90°, V = 2728.36 (56) Å3, Z = 4,
References
D
calcd = 1.136 Mg/m–3, F(000) = 1008, T = 286 (2) K. All
(1) Vicinal amines are important chiral auxiliaries. For excellent
reviews, see: (a) Lucet, D.; Le Gall, T.; Mioskowski, C.
Angew. Chem. Int. Ed. 1998, 37, 2580. (b) Bennani, Y. L.;
Hanessian, S. Chem. Rev. 1997, 97, 3161.
(2) (a) Neumann, W. L.; Rogic, M. M.; Dunn, T. J. Tetrahedron
Lett. 1991, 32, 5865. (b) Alvaro, G.; Savoia, D. Synlett
2002, 651.
non-hydrogen atoms were refined anisotropically, whereas
the hydrogen atoms were generated geometrically. Final R
indices [I>2s(I)]: R1 = 0.0415, wR2 = 0.0788.
Crystallographic data has been deposited with the
Cambridge Crystallographic Data Center supplementary
publication no. CCDC-275776. Copies of the data can be
obtained free of charge on application to CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK [fax: +44 (1223)762910;
e-mail: deposit@ccdc.cam.ac.uk].
Synlett 2005, No. 18, 2776–2780 © Thieme Stuttgart · New York