A. Alexakis et al. / Tetrahedron: Asymmetry 12 (2001) 1171–1178
1177
2
0
1
oil (3.25 g, 72%); [h] =−82.7 (c 1.15, CHCl );
H
sium carbonate (5 g) in anhydrous ethanol was added
cyclohexene oxide (3.5 g, 35 mmol). After stirring the
solution under reflux for 48 h under a nitrogen atmo-
sphere, the salts were eliminated by filtration and the
solvent was evaporated. The crude product was dis-
solved in ether (150 mL) and washed with a saturated
potassium carbonate solution. This aqueous phase was
washed with ether and then with dichloromethane. The
organic layers were dried over K CO and the solids
removed by filtration. The filtrate was evaporated. The
viscous brown oil contained an alcohol resulting from
the opening of the epoxide, which was separated by
distillation under reduced pressure (35°C, 0.3 mbar).
The resulting solid distillation residue was dissolved in
acetone, giving after standing for 24 h in a refrigerator
D
3
NMR (CDCl ): l 2.26 and 1.91 (m, 4H, NH-(CH
)-NH-), 2.36, 2.08, 1.92, 1.81, 1.24–1.22 (m,
H, NH-(CH-(CH ) -CH)-NH-), 1.80 (m, 2H, CH2-
SiMe ), 0.05 (s, 9H, CH -SiMe ); C NMR (CDCl ): l
(NH -(CH-CH -(CH ) -CH -C
SiMe ), 36.44 and 35.85 (NH -(C
6
-
3
(
8
CH ) -CH
6
2
4
6
6
2
4
1
3
3
2
3
3
6
7.48
6
H)-NH-CH2-
2
2
2 2
6
2
H-CH -(CH ) -C
6
H2-
3
2
2
2 2
CH)-NH-CH -), 25.37 and 25.25 (NH -(CH-CH -
(C6 H ) -CH -CH)-NH-CH -SiMe ), 54.82 (C6 H -SiMe ),
2 2 2 2 3 2 3
2
2
2
2
3
−
2.68 (CH -SiMe ).
2 3
4
.13. (R,R)-N,N%-Dibenzylcyclohexane-1,2-diamine 13
(
R,R)-N,N%-Dibenzylcyclohexane-1,2-diamine 13 was
synthesised according to the procedure described above
with benzyl chloride (5.8 mL, 2.1 equiv.), K CO (15 g),
potassium iodide (0.5 g) and (R,R)-1,2-diammoniumcy-
clohexane mono-(+)-tartrate salt 4 (6 g, 22.7 mmol).
The reaction mixture was stirred at rt for 140 h. After
distillation (150°C, 0.4 mbar) a colourless oil was recov-
ered, which solidified upon standing (3.4 g, 51%); mp
2
3
and filtration, a white crystalline solid (1.6 g, 63%); mp
+
7
[
8–80°C; MS (electrospray) m/z=311.23 [(MH) ];
20
1
h] =−8.3 (c 1.3, CHCl ); H NMR (CDCl ): l 1.05
D
3
3
(
4
m, 4H, -NH-(CH-CH2
H, NH-(CH-CH2-(CH ) -CH
NH-(CH-CH -(CH ) -C
6
-(CH ) -CH
6
2-CH)-OH), 1.20 (m,
2 2
6
6 -CH)-NH), 1.29 (m, 4H,
2 2
2
-
-
6
H -CH)-OH), 1.66 (m, 4H,
2
2 2
2
1
1
3
2
−
7–38°C (lit. 36–37°C); MS (electrospray) m/z=
NH-(CH-CH -CH -CH
6
-CH -CH)-OH), 1.66 (m, 4H,
2
2
2
2
+
20
D
20
D
31.15 [(MH) ]; [h] =−68 (c 1.3, CHCl ) (lit. [h] =
3
-NH-(CH-CH -(CH
6
) -CH -CH)-OH), 2.02 (m, 4H,
2
2 2
2
1
67 (c 1.15, CHCl )); H NMR (CDCl ): l 1.11, 1.26,
3
3
-NH-(CH-CH -CH
6
-CH -CH -CH)-OH), 2.34 (m, 4H,
-CH -(CH ) -CH -CH
2
2
2
2
1
.75 and 2.19 (m, 8H, -NH-(CH-(CH2
.00–2.30 (m, 4H, -N-CH ), 2.28 (m, 2H, NH-(CH
)-NH-), 3.91 (d, 2H, CH Ph),
.32–7.36 (m, 10H, Harom); C NMR (CDCl ): l 24.98
6 )4-CH)-NH),
-NH-(CH
6
6
)-NH), 2.48 (m, 4H,
2
2 2
2
2
6
-
2
NH-(CH-CH -(CH ) -CH -CH)-OH), 3.45 (m, 2H,
CH-OH); C NMR (CDCl ): l 24.33, 25.45, 25.58
6
2
2 2
2
CH -(CH ) -CH -CH
7
6
13
2
2 2
2
2
1
3
3
3
(
(
(
(
(
-NH - (CH - CH - ( C6 H ) - CH - CH) - NH - (CH - CH -
2 2 2 2 2
C6 H ) -CH -CH)-OH), 30.86, 32.56, 33.19, 35.25
2 2 2
(
-NH-(CH-CH -( C6 H ) -CH -CH)-NH-), 31.40 (-NH-
2 2 2 2
(CH-C
6
H -(CH ) -C
6
H -CH)-NH-), 50.26 (-NH-(C
6
H-
2
2 2
2
-NH - (CH - C
6
H - (CH ) - C
6
H - CH) - NH - (CH - C
6
H2-
2
2 2
2
CH -(CH ) -CH -C
6 H)-NH-), 58.74 (CH O), 61.61
2
2 2
2
3
CH ) -C
6
H -CH)-OH), 65.43, 65.58 (-NH-(C
6
H-CH -
2
2
2
2
(
1
-NHCH ), 72.40 (CH O), 60.60 (-CH Ph), 140.88,
2 2 2
CH ) -CH -C
6
H)-NH-C
6
H-CH -(CH ) -CH -C
6
H)-OH).
2
2
2
2
2 2
2
28.28, 127.88, 126.4 (Carom).
4.14. (R,R)-N,N%-Diallylcyclohexane-1,2-diamine 14
References
According to the general procedure, allyl chloride (4
mL, 2.8 equiv.) or allyl bromide (4.35 mL, 2.8 equiv.)
were stirred with K CO (15 g) and potassium iodide
1
2
. (a) Bennani, Y. L.; Hanessian, S. Chem. Rev. 1997, 97,
161; (b) Lucet, D.; Le Gall, T.; Mioskowski, C. Angew
Chem. 1998, 110, 2724–2772; Angew Chem., Int. Ed. 1998,
7, 2580–2627; (c) Fache, F.; Schulz, E.; Tommassino,
M.; Lemaire, M. Chem. Rev. 2000, 100, 2159.
. Alexakis, A.; Mangeney, P. In Advanced Asymmetric
Synthesis; Stephenson, G. R., Ed.; Chapman & Hall:
London, 1996; Chapter 5, p. 93.
3
2
3
(
(
0.5 g) and (R,R)-1,2-diammoniumcyclohexane mono-
+)-tartrate salt 4 (6 g, 22.7 mmol) at rt for 140 h,
3
giving after distillation (52°C, 0.3 mbar), (R,R)-N,N%-
dibenzylcyclohexane-1,2-diamine 14 (2.4 g, 55%);
2
0
1
[
h] =−10.2 (c 1.4, CHCl ); H NMR (CDCl ): l 1.06
D
3
3
(
(
(
(
(
(
m, 4H, NH-(CH-CH2
6
-(CH ) -CH
6
2-CH)-NH-), 1.70
2-CH)-NH-), 2.97
2 2
3
4
. Alexakis, A.; Mutti, S.; Mangeney, P. J. Org. Chem.
m, 4H, NH-(CH-CH
m, 2H, NH-(CH
m, 2H, -CH -CHꢀCH ), 5.11 (dd, 2H, -CHꢀCH
m, 4H, -CH
CH-CH -(CH ) -CH -CH)-NH-), 26.67 (NH-(CH-
6
-(CH ) -CH
6
2
2 2
1992, 57, 1224.
6
-CH -(CH ) -CH -CH
6
)-NH-), 3.31
2), 5.83
6 ꢀCH ); C NMR (CDCl ): l 25.91 (NH-
2
2 2
2
. (a) Kazuhiro, N.; Kazuo, K.; Junnosoka, F. Chem. Lett.
1978, 489; (b) Fiorini, M.; Giongo, G. M. J. Mol. Cat.
6
6
2
2
1
3
2
3
1979, 5, 303; (c) Hanessian, S.; Delorme, D.; Beaudoin,
6
2
2 2
2
S.; Leblanc, Y. J. Am. Chem. Soc. 1984, 106, 5754; (d)
Bennani, Y. L.; Hannessian, S. Tetrahedron 1996, 44,
C6 H -(CH ) -C6 H -CH)-NH-), 52.77 (- C6 H -CHꢀCH ),
2 2 2 2 2
2
5
(
9.37 (NH-(C
6 H-CH -(CH ) -CH - C6 H)-NH-), 115.58
2 2 2 2
13837.
-CHꢀCH ), 138.56 (-C
6
6
HꢀCH2).
2
5
6
. (a) Gasbøl, F.; Steenbøl, P.; Sørensen, B. S. Acta Chem.
Scand. 1972, 26, 3605; (b) Larrow, J. F.; Jacobsen, E. N.
J. Org. Chem. 1994, 59, 1939.
. Mutti, S. Ph.D. Thesis; University Pierre et Marie Curie:
Paris, 1991.
4
.15. N,N%-Bis(2-hydroxycyclohexyl)-trans-cyclohexane-
1
,2-diamine 16
This procedure is a modification of that reported by
1
2
7. Alexakis, A.; Kanger, T.; Mangeney, P.; Rose-Munch,
Hancock et al.
.
F.; Perrotey, A.; Rose, E. Tetrahedron: Asymmetry 1995,
6
, 2135.
To a suspension of (R,R)-1,2-diammoniumcyclohexane
mono-(+)-tartrate salt 4 (2.3 g, 8.8 mmol) and potas-
8
. Tierney, J. P.; Alexakis, A.; Mangeney, P. Tetrahedron:
Asymmetry 1997, 8, 1019.