K. Sato et al. / Tetrahedron Letters 45 (2004) 1523–1525
1525
OTs
HO
HO
O
O
a
b
c
HO
Me
12
Me
BocHN
OMe
BocHN
OMe
13
14
MeO
Me
O
Me
Me
Me
O
O
O
HO
Me
d
Ref. 12
Me
4 steps
46%
OH
BocHN
OMe
NO2
BocHN
OMe
D-Rubranitrose
15
16
Scheme 2. Reagents and conditions: (a) 95% AcOH aq (93%); (b) TsCl/Py (90%); (c) NaBH4/DMSO (89%); (d) (COCl)2, DMSO, Et3N/CH2Cl2
(76%).
tion of the methanesulfonyloxymethyl branched-chain
amino derivative,19 did not occur under these reaction
conditions (Fig. 2). Usually the reductive ring opening
of the aziridine ring is achieved under more drastic
condition, for example, using an autoclave. Therefore
this method for constructing methyl branched-chain
amine structure should be very useful for large-scale
synthesis. Interestingly, in the case of the 3-epimer of 10
having the axial methanesulfonyloxymethyl branched
chain and the equatorial azide group, the same reaction
conditions did not give the corresponding methyl
branched-chain amino derivative but a spiroaziridine
derivative.19 The branched-chain compound 12 was then
hydrolyzed with 95% AcOH aq for 48 h to give the
deprotected diol 13 (syrup) in 93% yield. A selective
tosylation of 13 with TsCl in pyridine at rt gave the
corresponding 6-O-tosylate 14 (syrup) in 90% yield. The
compound 14 was derived into the corresponding
6-deoxy derivative 15 (syrup) in 89% yield by NaBH4/
DMSO.15 Then, Swern oxidation17 of 15 gave the known
carbonyl compound 1612 in 76% yield (Scheme 2). The
physical constants of 16 were completely identical with
that reported.12 The further transformation of 16 into
References and notes
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D
-rubranitrose has been reported by Klemer and Wil-
D
bers12 in 1987. As a result the synthesis of
nitrose in 22 steps was successfully and conveniently
accomplished. The overall yield from 1 was 4.9%.
-rubra-
12. Klemer, A.; Wilbers, H. Liebigs Ann. Chem. 1987, 10, 815–
823.
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Acknowledgements
This work was partially supported by a ÔHigh-Tech
Research Center ProjectÕ and a Grant-in-Aid (15750148)
for Scientific Research from the Ministry of Education,
Science, Sports and Culture, Japan. The author thanks
Professor T. Nakagawa for helpful discussions.
16. Evans, M. E. Carbohydr. Res. 1972, 21, 473–475.
17. Mancuso, A. J.; Swern, D. Synthesis 1985, 165–185.
18. Baker, D. C.; Brown, D. K.; Horton, D.; Nikol, R. G.
Carbohydr. Res. 1974, 32, 299–319.
19. Our unreported results.