D. Rodríguez et al. / Tetrahedron Letters 49 (2008) 6866–6869
6869
10. Tsuchiya, S.; Sunazuka, T.; Hirose, T.; Mori, R.; Tanaka, T.; Iwatsuki, M.; Omura,
M. Org. Lett. 2006, 8, 5577–5580.
11. Caron, M.; Carlier, P. R.; Sharpless, K. B. J. Org. Chem. 1988, 53, 5185–5187.
12. Achmatowicz, M.; Hegedus, L. S. J. Org. Chem. 2004, 69, 2229–2234.
13. Lee, M.; Lee, T.; Kim, E.-Y.; Ko, H.; Kim, D.; Kim, S. Org. Lett. 2006, 8, 745–748.
14. Picó, A.; Moyano, A. Arkivoc 2007, 132–156.
the pyrrolidine analog 2, potentially useful intermediates for the
preparation of N-heterocyclic natural products such as (+)-a-
conhydrine.
Acknowledgments
15. Wertheim, T. Liebigs Ann. Chem. 1856, 100, 328–330.
16. Späth, E.; Adler, E. Monatsh. Chem. 1933, 63, 127–140.
We thank the Spanish Ministry of Science and Education for
financial support (Projects BQU2003-03426 and AYA2006-15648-
C02-01). A.P. thanks the University of Barcelona for a predoctoral
fellowship.
17. For some leading references, see: (a) Masaki, Y.; Imaeda, T.; Nagata, K.; Oda, H.;
Ito, A. Tetrahedron Lett. 1989, 30, 6395–6936; (b) Guerreiro, P.;
Ratovelomanana-Vidal, V.; Genêt, J.-P. Chirality 2000, 12, 408–410; (c)
Comins, D. L.; Williams, A. L. Tetrahedron Lett. 2000, 41, 2839–2842; (d)
Enders, D.; Nolte, B.; Raabe, G.; Runsink, J. Tetrahedron: Asymmetry 2002, 13,
285–291; (e) Kandula, S. V.; Kumar, P. Tetrahedron Lett. 2003, 44, 1957–1958;
(f) Pandey, S. K.; Kumar, P. Tetrahedron Lett. 2005, 46, 4091–4093; (g) Chang,
M.-Y.; Kung, Y.-H.; Chen, S.-T. Tetrahedron 2006, 63, 10843–10848; (h)
Voituriez, A.; Ferreira, F.; Chemla, F. J. Org. Chem. 2007, 72, 5358–5361; (i)
Jamieson, A. G.; Sutherland, A. Org. Lett. 2007, 9, 1609–1611.
References and notes
1. (a) Elbein, A. D.; Molyneux, R. J. In Alkaloids: Chemical and Biological Perspective;
Pelletier, J. W., Ed.; Wiley: New York, 1986; Vol. 5, pp 1–54; (b) Casiraghi, C.;
Zanardi, F.; Rassu, G.; Spanu, P. Chem. Rev. 1995, 95, 1677–1716; (c) Michael, J.
P. Nat. Prod. Rep. 1997, 14, 619–636.
2. (a) See inter alia: Tamoto, K.; Ohuchi, R.; Ono, K. Eur. Pat. Appl. 44, 1987.; (b)
Pallavicini, M.; Moroni, B.; Bolchi, C.; Cilia, A.; Clementi, F.; Fumagalli, L.;
Gotti, C.; Meneghetti, F.; Riganti, L.; Vistoli, G.; Valoti, E. Bioorg. Med. Chem. Lett.
2006, 16, 5610–5615; (c) Scapecchi, S.; Matucci, R.; Bellucci, C.; Buccioni, M.;
Dei, S.; Guandalini, L.; Martelli, C.; Manetti, D.; Martini, E.; Marucci, G.; Nesi,
M.; Romanelli, M. N.; Teodori, E.; Gualtieri, F. J. Med. Chem. 2006, 49, 1925–
1931.
18. Nagata, K.; Toriizuka, Y.; Itoh, T. Heterocycles 2005, 65, 107–109.
19. Physical data of representative compounds: Compound 12: [
CH2Cl2). IR (NaCl film) max = 3330, 2954, 2931, 2860, 1702, 1534, 1472, 1457,
1389, 1256, 1097, 837, 776 cmꢀ1 1H NMR (200 MHz, CDCl3): d 7.35–7.29 (m,
a
]
D
ꢀ5.4 (c 1.02,
m
.
5H), 5.06 (m, 2H), 4.68 (d, J = 6.8 Hz, 1H), 3.67–3.37 (m, 3H), 2.89–2.65 (m, 3H),
1.73–1.11 (m, 6H), 0.85 (s, 9H), 0.01 (s, 6H). 13C NMR (50 MHz, CDCl3): d 156.0
(C), 136.0 (C), 128.5 (CH), 128.0 (CH), 66.9 (CH2), 62.9 (CH2), 53.9 (CH), 46.1
(CH2), 32.4 (CH2), 31.5 (CH2), 26.0 (CH3), 22.0 (CH2), 18.4 (C), ꢀ5.2 (CH3). MS
(CI, NH3): m/z = 411 ([M+18]+, 10%), 394 ([M+1]+, 100%). HRMS (ESI-TOF): m/z
calcd for C21H36NO4Si: 394.2414; found for [M+1]+: 394.2414. Compound 1:
[
a
]
D ꢀ19.0 (c 1.05, CH2Cl2). IR (NaCl film)
mmax = 2941, 2860, 1700, 1416, 1355,
3. Woodin, K. S.; Jamison, T. F. J. Org. Chem. 2007, 72, 7451–7454.
4. (a) Busqué, F.; de March, P.; Figueredo, M.; Font, J.; Sanfeliu, E. Tetrahedron Lett.
2002, 43, 5583–5585; (b) Blanco, P.; Busqué, F.; de March, P.; Figueredo, M.;
Font, J.; Sanfeliu, E. Eur. J. Org. Chem. 2004, 48–53.
5. (a) Castejón, P.; Pastó, M.; Moyano, A.; Pericàs, M. A.; Riera, A. Tetrahedron Lett.
1995, 36, 3019–3022; (b) Castejón, P.; Moyano, A.; Pericàs, M. A.; Riera, A.
Tetrahedron 1996, 52, 7063–7086; (c) Aguilar, N.; Moyano, A.; Pericàs, M. A.;
Riera, A. J. Org. Chem. 1998, 63, 3560–3567; (d) Aguilar, N.; Moyano, A.; Pericàs,
M. A.; Riera, A. Tetrahedron Lett. 1999, 40, 3913–3916; (e) Catasús, M.; Moyano,
A.; Pericàs, M. A.; Riera, A. Tetrahedron Lett. 1999, 40, 9309–9312; (f) Picó, A.;
Moyano, A.; Pericàs, M. A. J. Org. Chem. 2003, 68, 5075–5083.
1310, 1256, 1156, 899, 855 cmꢀ1 1H NMR (400 MHz, CDCl3): d 7.40–7.25 (m,
.
5H), 5.20–5.10 (m, 2H), 4.15 (m, 1H), 3.95 (m, 1H), 3.18–3.15 (m, 1H), 3.00 (td,
J = 13.2 Hz, J0 = 2.4 Hz, 1H), 2.74 (t, J = 4.8 Hz, 1H), 2.66 (m, 1H), 1.85–1.82 (m,
1H), 1.72–1.67 (m, 5H). 13C NMR (100 MHz, CDCl3): d 155.5 (C), 136.6 (C), 128.5
(CH), 128.0 (CH), 127.9 (CH), 67.2 (CH2), 52.5 (CH), 50.9 (CH), 46.8 (CH2), 41.3
(CH2), 25.7 (CH2), 25.0 (CH2), 19.6 (CH2). MS (CI, NH3): m/z = 279 ([M+18]+,
15%), 262 ([M+1]+, 58%), 172 ([Mꢀ72]+, 100%). HRMS (ESI-TOF): m/z calcd for
C15H20NO3: 262.1443; found for [M+1]+: 262.1440. Compound 16: [
a
]
D
ꢀ11.6
(c 1.10, CHCl3). IR (NaCl film)
mmax = 3323, 3064, 2931, 1694, 1538, 1455, 1258,
1050, 739 cmꢀ1 1H NMR (400 MHz, CDCl3): d 7.36–7.32 (m, 5H), 5.09 (m, 2H),
.
5.04 (br d, 1H), 3.64 (t, J = 5.4 Hz, 2H), 3.54 (m, 1H), 2.89 (m, 1H), 2.76 (m, 2H),
1.99 (br s, 1H), 1.75–1.54 (m, 4H). 13C NMR (100 MHz, CDCl3): d 156.2 (C),
136.3 (C), 128.5 (CH), 128.2 (CH), 128.1 (CH), 66.9 (CH2), 62.2 (CH2), 53.9 (CH),
52.3 (CH), 46.1 (CH2), 28.3 (CH2), 28.1 (CH2). MS (CI, NH3): m/z = 283 ([M+18]+,
20%), 266 ([M+1]+, 63%), 222 ([Mꢀ43]+, 100%). HRMS (ESI-TOF): m/z calcd for
6. (a) Hanson, R. M.; Sharpless, K. B. J. Org. Chem. 1986, 51, 1922–1925; (b) Gao, Y.;
Hanson, R. M.; Klunder, J. M.; Ko, S. Y.; Masamune, H.; Sharpless, K. B. J. Am.
Chem. Soc. 1987, 109, 5765–5780; (c) Katsuki, T.; Martín, V. S. Org. React. 1996,
48, 1–299; (d) Xia, Q.-H.; Ge, H.-Q.; Ye, C.-P.; Liu, Z.-M.; Su, K.-X. Chem. Rev.
2005, 105, 1603–1662.
7. For other efficient asymmetric approaches to 2-(1-aminoalkyl)oxiranes, see: (a)
Concellón, J. M.; del Solar, V.; García-Granda, S.; Díaz, M. R. J. Org. Chem. 2007,
72, 7567–7573; (b) Concellón, J. M.; del Solar, V.; Suárez, J. R.; Blanco, E. G.
Tetrahedron 2007, 63, 2805–2810.
8. (a) Nicolaou, K. C.; Prasad, C. V. C.; Somers, P. K.; Hwang, C.-K. J. Am. Chem. Soc.
1989, 111, 5335–5340; See also: (b) Guay, B.; Deslongchamps, P. J. Org. Chem.
2003, 68, 6140–6148.
9. (a) Nacro, K.; Baltas, M.; Gorrichon, L. Tetrahedron 1999, 55, 14013–14030; (b)
Nicolaou, K. C.; Hwang, C.-K.; Marron, B. E.; De Fries, J. A.; Couladros, E. A.; Abe,
Y.; Carroll, P. J.; Snyder, J. P. J. Am. Chem. Soc. 1990, 112, 3040–3054.
C14H20NO4: 266.1392; found for [M+1]+: 266.1387. 2: [
a
]
D
ꢀ11.7 (c 1.00,
CHCl3). IR (NaCl film)
mmax = 2958, 2881, 1702, 1455, 1411, 1357, 1191, 1106,
699 cmꢀ1 1H NMR (400 MHz, CDCl3): d 7.38–7.34 (m, 5H), 5.15 (m, 2H), 5.04
.
(br d, 1H), 3.72 (m, 1H), 3.50 (m, 2H), 3.03–2.50 (m, 3H), 1.95–1.90 (m, 4H). 13C
NMR (100 MHz, CDCl3): d (mixture of rotamers) = 157.2 (C), 136.8 (C), 128.5
(CH), 128.2/128.1 (CH), 127.9/127.8 (CH), 67.1/66.7 (CH2), 59.1/58.5 (CH), 52.9/
52.5 (CH), 47.6/47.4 (CH2), 47.2/46.7 (CH2), 28.6/27.3 (CH2), 24.1/23.2 (CH2).
MS (CI, NH3): m/z = 265 ([M+18]+, 26%), 248 ([M+1]+, 100%), 204 ([Mꢀ43]+, 7%).
HRMS (ESI-TOF): m/z calcd for C14H18NO3: 248.1287; found for [M+1]+:
248.1281.