J. Lee et al. / Tetrahedron Letters 42 (2001) 6223–6225
6225
Acknowledgements
Pohl, S.; Martens, J. Liebigs Ann. 1997, 576; (c) Cossy, J.;
Dumas, C.; Michel, P.; Pardo, D. G. Tetrahedron Lett.
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Chem. 1984, 49, 40; (e) Hammer, C. F.; Heller, S. R.;
Craig, J. H. Tetrahedron 1972, 28, 239.
We wish to thank to Chris Welch for assistance with
the chiral HPLC assays and Bob Reamer for NMR
studies.
9. (a) Jacobsen, E. J.; Zhang, W.; Muci, A. R.; Ecker, J. R.;
Deng, L. J. Am. Chem. Soc. 1991, 113, 7063; (b) Zhang,
W.; Jacobsen, E. N. J. Org. Chem. 1991, 56, 2296. For
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Synthesis; Ojima, I., Ed.; VCH: New York, 1993; Chap-
ter 4.2.
References
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For the reaction condition; N-phenylpyridine-N-oxide
(PPO), (R,R)-(−)-N,N%-bis(3,5-di-tert-butylsalicylidene)-
1,2-cyclohexanediaminomanganese(III) chloride, methyl-
ene chloride, NaCl, NaOCl (13%), 5°C for 48 h (assay
conditions: (S,S) Whelko column, 0.5% i-PrOH/hexanes;
1.0 ml/min, 20°C; 250 nm).
3. (a) Baker, R.; Cutis, N. R.; Elliott, J. M.; Harrison, T.;
Hollingworth, G. J.; Jackson, P. S.; Kulagowski, J. J.;
Seward, E. M.; Swain, C. J.; Williams, B. J. Int. Patent
WO97/49710, 1997; (b) Kulagowski, J. J.; Curtis, N. R.;
Swain, C. J.; Williams, B. J. Org. Lett. 2001, 3, 667–670;
(c) Maligres, P. E.; Waters, M. S.; Lee, J.; Reamer, R.;
Askin, D.; Ashwood, M. S.; Cameron, M. J. Org. Chem.,
submitted; (d) see also: Wallace, D. J.; Goodman, J. M.;
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Lett. 2001, 3, 671–674.
4. For the utilization of chiral pool precursors, see: (a)
Calvez, O.; Langlois, N. Tetrahedron Lett. 1999, 40, 7099.
For the previous catalytic asymmetric synthesis using
Sharpless’ dihydroxylation, see: (b) Stadler, H.; Bos, M.
Heterocycles 1999, 51, 1067. For the racemic synthesis/
resolution, see: (c) Tomooka, K.; Nakazaki, A.; Nakai,
T. J. Am. Chem. Soc. 2000, 122, 408.
5. Baldwin, J. E. J. Chem. Soc., Chem. Commun. 1976, 734.
6. (a) Mukai, C.; Sugimoto, Y.; Miyazawa, K.; Yamaguchi,
S.; Hanaoka, M. J. Org. Chem. 1998, 63, 6281. For
examples of asymmetric epoxide opening in ‘6-endo
mode’ using cationic-olefin cyclization, see: (b) Corey, E.
J.; Lee, J. J. Am. Chem. Soc. 1993, 115, 8873; (b) Corey,
E. J.; Lee, J.; Liu, D. R. Tetrahedron Lett. 1994, 35, 9149;
(c) Huang, A. X.; Xiong, Z.; Corey, E. J. J. Am. Chem.
Soc. 1999, 121, 9999.
7. (a) Intramolecular opening of the cis-b-alkylstyrene oxide
in ‘6-endo mode’ was attempted with nitrogen nucle-
ophiles (6P; trifluoroacetamide or p-methoxy benzyl
amine); (b) for conformational effects of cis-b-alkyl sty-
rene oxide, see: (a) Brown, H. C.; Narasimhan, S.;
Somayaji, V. J. Org. Chem. 1983, 48, 3091; (b) Brandes,
B. D. Ph.D Thesis, Harvard University, 1998.
10. (a) Cossy, J.; Dumas, C.; Pardo, D. G. Eur. J. Chem.
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11. Aziridium intermediate 11 could be isolated by trituation
of hexanes at −20°C. For the experimental details of ring
expansion; N-benzyl-hydroxy-pyrrolidine 10 (6.65 g, 22.4
mmol) was placed in dry THF (110 ml) and cooled to
−20°C. Methanesulfonyl chloride (2.08 mL, 26.9 mmol)
was introduced into the solution followed by triethyl-
amine (12.5 mL, 89.6 mmol). The resulting solution was
aged for 1 h at this temperature. Tetra-n-butylammonium
acetate (39 g, 129 mmol) was added and the resulting
mixture was warmed to room temperature over a period
of 1 h. After aging for 16 h at room temperature, the
reaction mixture was extracted with EtOAc (2×200 mL)
and washed sequentially with 100 mL of sat. NaHCO3,
and 50 mL of saturated aq NaCl. After concentration of
the organic layer, the crude mixture was purified by flash
chromatography on silica gel (hexanes–EtOAc, 9:1 (v/v)
gradient to 7:3 (v/v)) followed by recrystallization from
EtOAc–hexanes to afford the desired 3-acetoxypiperidine
12 in 85% yield with 99% ee (assay conditions: SFC
method, Chiralcel OJ column, 4% MeOH in CO2, 300
bar, 35°C, 1.5 mL/min at 215 nm); mp 105–106°C; 1H
NMR (CDCl3, 400 MHz) l 1.55 (m, 1H), 1.56 (m, 1H),
1.93 (s, 3H), 2.06 (m, 3H), 2.95 (d, 1H), 3.05 (d, 1H), 3.41
(d, 1H), 3.84 (d, 1H), 5.03 (d, 1H), 7.28 (m, 8H), 7.47 (d,
2H); 13C NMR (CDCl3, 100 MHz) l 20.5, 21.1, 29.4,
52.8, 59.7, 70.3, 71.7, 126.8, 127.4, 128.1, 128.1, 128.7,
128.9, 170.2.
12. The identity of 3 was confirmed by comparison with
authentic material (Ref. 2b).
13. Pfitzner, K. E.; Moffatt, J. G. J. Am. Chem. Soc. 1965,
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(b) Wilken, J.; Kossenjans, M.; Saak, W.; Haase, D.;