C. A. Busacca et al. / Tetrahedron: Asymmetry 11 (2000) 1907±1910
1909
mmol, 2.5 equiv.) was slowly added. The yellow solution was allowed to slowly warm to ambient
temperature. After 3 h, the reaction mixture was concentrated in vacuo and the residue chroma-
tographed on silica gel eluting with 3:1 hexane:EtOAc to give 1.65 g (85%) of 4 as a colorless
ꢀ
1
solid, m.p. 146±147 C; [ꢁ] = +48.7 (c 0.46, CHCl ); H NMR (400 MHz, CDCl ) ꢀ: 7.82 (dd,
D
3
3
J=5.4, 3.0 Hz, 2H), 7.67 (dd, J= 5.5, 3.1 Hz, 2H), 4.46 (br d, J=10.6 Hz, 1H), 3.84 (dd, J=12.2,
2
13
.9 Hz, 1H), 3.79 (dd, J=10.7, 3.0 Hz, 1H), 3.62 (m, 1H), 1.10 (s, 9H), 1.02 (s, 9H). C NMR
(
100 MHz, CDCl ) ꢀ: 168.86 (s), 156.42 (s), 134.14 (d), 132.58 (s), 123.53 (d), 79.32 (s), 57.90 (d),
3
39.04 (t), 34.06 (s), 28.20 (q), 26.85 (q). Anal. calcd for C H N O : C, 65.88; H, 7.56; N, 8.09.
19 26 2 4
Found: C, 65.96; H, 7.53; N, 8.00.
3
.3. BOC-diamine 5
A ¯ask with re¯ux condenser was charged with 1.60 g 4 (4.62 mmol, 1 equiv.), 40 mL EtOH
and 1.31 mL N H hydrate (CAUTION: toxic; 23.1 mmol, 5 equiv.) in the order given. The
mixture was re¯uxed for 45 min, cooled and ®ltered, and the solids washed well with Et O. The
2
4
2
®
ltrate was washed with H O, dried (K CO ) and concentrated in vacuo to a light orange solid.
2 2 3
ꢀ
Recrystallization (hexane) aorded 840 mg (84%) of 5 as a colorless solid, m.p. 84 C; [ꢁ] = +9.8
D
1
3 3
(c 0.48, CHCl ); H NMR (400 MHz, CDCl ) ꢀ: 4.59 (br d, J=10.2 Hz, 1H), 3.23 (br t, J=9.0
13
Hz, 1H), 2.85 (d, J=13.3 Hz, 1H), 2.30 (br t, J=12.1 Hz, 1H), 1.35 (s, 9H), 0.81 (s, 9H).
C
NMR (100 MHz, CDCl ) ꢀ: 156.78 (s), 78.86 (s), 62.40 (d), 42.26 (t), 34.10 (s), 28.32 (q), 26.50 (q).
3
Anal. calcd for C H N O : C, 61.07; H, 11.18; N, 12.95. Found: C, 61.22; H, 11.26; N, 12.91.
2
11
24
2
3
.4. Diamine dihydrochloride 1
Compound 5 (690 mg, 3.19 mmol, 1 equiv.) was dissolved in 12 mL MeOH, then 3.19 mL 4N
HCl/p-dioxane (12.8 mmol, 4 equiv.) was added and the resulting mixture stirred for 5 h at
ambient temperature under N . The reaction mixture was concentrated in vacuo, and the resulting
2
solids ®ltered under N washing well with Et O to give 620 mg (99%) of 1 as a colorless solid,
2
2
ꢀ
1
m.p. 303 C (dec.); [ꢁ] = +14.6 (c 1.07, H O); H NMR (400 MHz, CDCl ) ꢀ: 8.61 (br s, 6H),
D
2
3
13
3
.20 (d, J=9.2 Hz, 1H), 3.19 (d, J=14.9 Hz, 1H), 2.94 (dd, J=14.3, 9.2 Hz, 1H), 0.96 (s, 9H). C
NMR (100 MHz, CDCl ) ꢀ: 58.36 (d), 39.35 (t), 33.44 (s), 26.22 (q). Anal. calcd for C H Cl N :
3
6
18
2
2
C, 38.10; H, 9.58; Cl, 37.49; N, 14.81. Found: C, 38.13; H, 9.77; Cl, 37.41; N, 14.81.
References
1
. For an excellent diamine review, see: Le Gall, T.; Mioskowski, C.; Lucet, D. Angew. Chem., Int. Ed. Engl. 1998,
7, 2580±2627.
. Katsuki, T. Coord. Chem. Rev. 1995, 140, 189±214.
. (a) Evans, D. A.; Lectka, T.; Miller, S. J. Tetrahedron Lett. 1993, 34, 7027. (b) Corey, E. J.; Sarshar, S.; Bordner, J.
J. Am. Chem. Soc. 1992, 114, 7938.
3
2
3
4
. (a) Sharpless, K. B.; Kolb, H. C.; VanNieuwenhze, M. S. Chem. Rev. 1994, 94, 2483. (b) Corey, E. J.; Jardine,
P. D.; Vigil, S.; Yuen, P.-W.; Connel, R. D. J. Am. Chem. Soc. 1989, 111, 9243.
5
6
7
. Kobayashi, S.; Takahashi, H.; Yoshioka, M.; Shibasaki, M.; Ohno, M.; Imai, N. Tetrahedron 1995, 51, 12013.
. Jacobsen, E. J.; Li, Z.; Conser, K. R. J. Am. Chem. Soc. 1993, 115, 5326.
. (a) Duchateau, A. L. L.; Guns, J. J.; Kubben, R. G. R.; van Tilburg, A. F. P. J. Chromatography A, 1994, 664,
1
69±176. (b) Garbarino, J. A. Ann. Chim. (Rome) 1969, 59, 841±846.
. (a) Hawkins, C. J.; Peachey, R. M. Aust. J. Chem. 1976, 29, 33±48. (b) Yanagihara, Y.; Yano, T.; Kobayashi, H.;
Ueno, K. Bull. Chem. Soc. Jpn. 1972, 45, 554±557.
8