asc.wiley-vch.de
7
2
.24 (m, 2 H), 4.03 (bs, 2 H), 2.18±2.15 (m, 2 H), 1.79 (bs,
1
3
H), 1.42±1.41 (m, 4 H);
3
C NMR (100 MHz, CDCl ):
d = 164.5, 149.8, 148.1, 136.9, 125.8, 122.0, 53.2, 32.6, 24.8;
HPLC (ChiralPak AD-RH 4.6 ´ 250 mm, flow rate = 0.5 mL/
min, water : acetonitrile, 1 : 1, detection at 210 nm); t
R
= 7.4
min (S,S-), t = 10.3 min (R,R-); anal. calcd. for C18H N O :
C, 66.65; H, 6.12; N, 17.27; found: C, 66.63; H, 6.24; N, 17.43.
R
20 4 2
Scheme 3.
Using this procedure, 2.5 kg of 1 were prepared in
86% yield with a > 99% ee. Easy access to these li-
gands will allow further exploration of other enantio-
selective transition metal-catalyzed allylic alkylation
reactions.
Acknowledgments
We are grateful to Dr. Bing Mao of our Analytical Research
Department for chiral HPLC analyses.
Experimental Section
References
General Remarks
(
1S, 2S)-(+)-1,2-Diaminocyclohexane and (1R, 2R)-(� )-1,2-
[
1] (a) B. M. Trost, C. Lee in Catalytic Asymmetric Syn-
diaminocyclohexane were purchased from Arran Chemical
nd
Company Limited. All other materials were obtained from
thesis, 2
ed., Ed. I. Ojima, Wiley-VCH, New York,
1
commercial suppliers and used without purification.
H
2000, 593±649; (b) A. Pfaltz, M. Lautens in Comprehen-
sive Asymmetric Catalysis, Eds. E. N. Jacobsen,
A. Pfaltz, H. Yamamoto, Springer, Berlin, 1999, Vol. 2,
13
NMR and C NMR spectra were recorded on a Bruker DPX-
00 spectrometer.
4
8
33±884; (c) S. J. Sesay, J. M. J. Williams in Advances in
(
(
S,S)-N,N'-Bis(2-pyridinecarboxamide)-1,2-cyclohexane
1)
A 22-L flask was charged with 1,1'-carbonyldiimidazole
1.70 kg, 10.48 mol) and anhydrous THF (KF < 50 lg/mL;
.5 L). Solid picolinic acid (1.36 kg, 11 mol) was added to
Asymmetric Synthesis, Ed. A. Hassner, JAI Press, Lon-
don, 1998, Vol. 3, 235±271; (d) B. M. Trost, D. L. Van
Vranken, Chem. Rev. 1996, 96, 395±422; (e) T. Hayashi
in Catalytic Asymmetric Synthesis, Ed. I. Ojima, Wiley-
VCH, New York, 1993, 325±365.
(
7
the slurry at room temperature. The resulting clear solution
[2] (a) T. Hayashi, M. Kawatsura, Y. Uozumi, J. Chem.
Soc., Chem. Commun. 1997, 561±562; (b) R. Pr e t oà t;
A. Pfaltz, Angew. Chem. Int. Ed. Engl. 1998, 37, 323±32
[3] (a) B. M. Trost, I. Hachiya, J. Am. Chem. Soc. 1998,
120, 1104±1105; (b) B. M. Trost, S. Hildbrand, K. Dogra,
J. Am. Chem. Soc. 1999, 121, 10416±10417; (c) F. Glor-
ius, A. Pfaltz, Organic Lett. 1999, 1, 141±144.
[4] D. J. Barnes, R. L. Chapman, R. S. Vagg, E. C. Watton,
J. Chem. Eng. Data 1978, 23, 349±350.
[5] H. Adolfsson, C. Moberg, Tetrahedron: Asymmetry
1995, 6, 2023±2031.
[6] Available in limited quantities from TCI America.
[7] K. V. Reddy, S-J. Jin, P. K. Arora, D. S. Sfeir, S. C. F. Ma-
loney, F. L. Urbach, L. M. Sayre, J. Am. Chem. Soc.
1990, 112, 2332±2340.
was stirred for 1 h at 18±20 °C and molten (1S, 2S)-(+)-1,2-
[
8]
diaminocyclohexane (0.5 g, 4.38 mol) was added over 1 h
while keeping the temperature below 50 °C. Additional
2
.5 L of THF were added as a rinse. The reaction mixture
was stirred at room temperature for 15 h. Water (0.5 L) was
added to the mixture and the solution was stirred for 1 h at
room temperature. The reaction mixture was concentrated
to an orange semi-solid by rotary evaporation. The semi-so-
lid residue was slurried in 5 L of ethanol and concentrated
by rotary evaporation. The resulting solid was dissolved in
ethanol (5 L) at 64±65 °C. The solution was allowed to slowly
cool to ±8 °C and the resulting white crystals were isolated by
filtration on a sintered glass funnel, washed with 5 L of cold
ethanol (� 8 to � 10 °C) and dried in a vacuum oven (35 °C).
The title compound 1 was isolated as a white crystalline so-
[8] (1S, 2S)-(+)-1,2-Diaminocyclohexane is a low melting
solid (mp = 40±43 °C). For ease of handling, the di-
amine was melted in a beaker on a hot plate and used
as a melt.
1
lid; yield: 1.23 kg (86.6%; 99.0% ee); mp 172±175 °C);
NMR (400 MHz, CDCl
J = 6.5 Hz, 2 H), 8.02±7.99 (m, 2 H), 7.69±7.64 (m, 2 H), 7.29±
H
3
): d = 8.50±8.49 (m, 2 H), 8.23 (d,
1
38
Adv. Synth. Catal. 2001, 343, 137±138