8
868
M. Shimizu, H. Makino / Tetrahedron Letters 42 (2001) 8865–8868
H
OOH
H
OOH
F3B
pAn N
pAn
H
H
pAnN
O2
N p
An
HNpAn
Ph
pAn N
p
N An
N
.
.
2
Ph
Ph
-H O
2 2
Ph
2
Ph
Ph
Ph
6
H O
2
2
O2
-
H O
H
OH
2
H
OH
pAnN
p
N An
pAn N
p
N An
.
.
Ph
Ph
Ph
Ph
7
Scheme 4.
hydroxyamine 7 may collapse to the imine 2 and water,
or may be oxidized to the hydroperoxyamine 6 (Scheme
4).
36, 1803–1804.
6. (a) House, H. O.; Berkowitz, W. F. J. Org. Chem. 1963,
28, 2271–2276; (b) Kovar, J. J.; Blaha, K. Coll. Czech.
Chem. Commun. 1963, 28, 2199–2206.
In conclusion, we have shown an oxidative cleavage of
,2-diamines and 1,2-amino alcohols in high yields
under very mild conditions. Since the cleaved products,
imine and/or aldehyde, may be used for further reac-
tions, the present reaction has a good potential for the
use of 1,2-diamines or amino alcohols as masked
diimines or imino carbonyl compounds.
7. Ogata, Y.; Sawaki, Y.; Shiroyama, M. J. Org. Chem.
1
1977, 42, 4061–4066.
8. Nagarkatti, J. P.; Ashley, K. R. Tetrahedron Lett. 1973,
14, 4599–4600.
9. Shimizu, M.; Iida, T.; Fujisawa, F. Chem. Lett. 1995,
609–610.
10. (a) Shimizu, M.; Kamei, M.; Fujisawa, T. Tetrahedron
Lett. 1995, 36, 8607–8610; (b) Shimizu, M.; Tsukamoto,
K.; Fujisawa, T. Tetrahedron Lett. 1997, 38, 5193–5196;
(c) Shimizu, M.; Fujisawa, T. J. Synth. Org. Chem. Jpn.
Acknowledgements
1998, 56, 672–680.
11. Shimizu, M.; Niwa, Y. Tetrahedron Lett. 2001, 42, 2829–
This research was supported by a Grant-in-Aid for
Scientific Research from the Ministry of Education,
Culture, Sports, Science and Technology, Japan, and a
grant from the Nagase Science and Technology
Foundation.
2832.
12. A typical procedure is as follows: To a solution of
1,2-diamine (1.0 equiv.) in CD CN (0.1 mmol/ml) was
added BF ·OEt (2.5 equiv.) at 0°C under an oxygen
3
3
2
atmosphere. After the disappearance of the 1,2-diamine
on TLC, the product yield was determined by 500 MHz
1
H NMR.
References
13. Typical procedure for oxidative cleavage of 1,2-amino
alcohols: To a solution of 1,2-amino alcohol (1.0 equiv.)
1
2
3
. Jackson, E. L. Org. React. 1944, 2, 341–375.
. Mosettiig, E. Org. React. 1954, 8, 225–229.
. Ohloff, G.; Giersch, W. Angew. Chem., Int. Ed Engl.
and MS4A (2.0 g/mmol) in CD
added BF ·OEt (2.5 equiv.) at 0°C under an oxygen
3
CN (0.1 mmol/ml) was
3
2
atmosphere. After the disappearance of the 1,2-amino
alcohol was monitored on TLC, the product yields were
1
973, 12, 401–402.
1
4. Cisneros, A.; Fernandez, S.; Hernandez, J. E. Synth.
determined by 500 MHz H NMR.
Commun. 1982, 12, 833–838.
. Gagnon, J. L.; Zajac, W. W., Jr. Tetrahedron Lett. 1995,
14. Buist, G. J.; Bunton, C. A.; Miles, J. H. J. Chem. Soc.
1959, 743–748.
5