S. Manabe et al. / Tetrahedron Letters 48 (2007) 787–789
789
Cl
O
S
Cl
O
Et3N
THF
O2
S
CO2H
O • N
+
N
H
O
Cl
Cl
Cl
Cl
5
6
7
Scheme 2. Preparation of anti-cancer reagent.
6. Go, A.; Kudo, S.; Takahashi, T.; Higure, R. Jpn. Pat.
06172323.
7. (a) Hohenlohe-Oehringen, K.; Call, L. Monatsh. Chem.
1968, 99, 1313–1319; (b) MacDonald, F. E.; Danishefsky,
S. J. J. Org. Chem. 1992, 57, 7001–7002.
It is possible to omit the aqueous work-up; the
compound can be purified directly after addition of
N,N0-dimethyl-1,3-propanediamine by silica gel column
chromatography.
8. (a) Hohenlohe-Oehringen, K.; Nedden, K.; Bertschneider,
H. Monatsh. Chem. 1972, 103, 1532–1533; (b) Richita, M.
A.; Slough, G. A. Tetrahedron Lett. 1993, 34, 6821–6824.
9. Ellis, D. Tetrahedron: Asymmetry 2001, 12, 1589–1593.
10. Wu, X.; Ro¨nn, R.; Gossas, T.; Larhed, M. J. Org. Chem.
2005, 70, 3094–3098.
11. Preparation of simple molecule tosyl sulfonamides using
p-toluenesulfonyl isocyanate are described very briefly in
the main text or in supporting materials in the below
references: (a) Feldman, K. S.; Bruendl, M. M.; Schild-
knegt, K.; Bohnstedt, A. C. J. Org. Chem. 1996, 61, 5440–
5452; (b) Trend, R. M.; Ramtohul, Y. K.; Ferreira, E. M.;
Stoltz, B. M. Angew. Int. Ed. 2003, 42, 2892–2895; (c)
Pinho, P.; Minnaard, A. J.; Feringa, B. L. Org. Lett. 2003,
5, 259–261.
Acknowledgments
We thank Dr. Teiji Chihara and his staff for elemental
analyses and Ms. Akemi Takahashi (RIKEN) for her
technical assistance. We also thank Dr. Yoshitaka
Hamashima (RIKEN) for HPLC help.
References and notes
1. (a) Lee, Y. K.; Bernstein, P. R.; Adams, E. J.; Brown, F.
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9
appeared at 1.45 ppm in CDCl3, whereas the methyl
signal of (R)-(a)-benzylmethyl amide 10 appeared at
1.43 ppm. The trials of HPLC ee determination of 2f
and 8 by chiral HPLC (CHIRALPAK AS-H, CHIR-
ALPAK AD-H, CHIRALCEL OD-H, CHIRALCEL
OJ-H, CHIRALPAK IA, CHIRALPAK IB, CHIRAL-
CEL OB, CHIRALPAK OT, CHIRALPAK OP) were failed.
Ph
Me3O•BF4
i-Pr2NEt
DMF
Me
NH2
i-Pr2NEt
O
Ph
O
TsHNOC
CO2Bn
NHCbz
DMF
86%
Ts
CO2Bn
CO2Bn
NHCbz
N
Me
N
95%
Me
H
NHCbz
Ph
2f
8
9
Me
NH2
89%
i-Pr2NEt
DMF
Ph
O
CO2Bn
NHCbz
Me
N
H
10
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