6006
A. F. Khlebnikov et al. / Tetrahedron Letters 45 (2004) 6003–6006
Bergman, R. J.; Tilley, T. D. J. Org. Chem. 2003, 68,
7.31 (m, 3H, H(Ph)), 7.38–7.44 (m, 2H, H(Ph)), 7.50–7.55
(m, 1H, H(Ph)), 7.73–7.76 (m, 2H, H(Ph)); 13C NMR
(75 MHz, CDCl3): 51.8 (MeO), 53.0 (MeO), 55.0 C3, 77.0
C2, 126.5, 127.8, 128.2, 128.3, 128.4, 130.4, 132.4, 138.8
C(Ph), 166.0 (C@O), 167.4 (C@O), 190.4 (C@N); Mass-
spectrum (EI, 70 eV), m=z (Im, %): 323 ([Mþ], 23), 264
([Mþ–CO2Me], 75), 204 ([Mþ–CO2Me–MeCO2H], 100),
188 (28), 178 (83), 105 (56), 77 (53); 6, mp 160 ꢁC (hexane–
9705–9710; (m) Li, G.-Y.; Chen, J.; Yu, W.-Y.; Hong, W.;
Che, C.-M. Org. Lett. 2003, 5, 2153–2156; (n) Galliford,
C. V.; Beenen, M. A.; Nguyen, S. T.; Scheidt, K. A. Org.
Lett. 2003, 5, 3487–3490; (o) Doyle, M. P.; Yan, M.; Hu,
W.; Gronenberg, L. S. J. Am. Chem. Soc. 2003, 125, 4692–
4693.
ꢀꢀ
6. (a) Palacios, F.; Ochoa de Retana, A. M.; Martynez de
Marigorta, E.; de los Santos, J. M. Org. Prep. Proced. Int.
2002, 34, 219–269; (b) Gilchrist, T. L. Aldrichim. Acta
2001, 34, 51–55; (c) Zwanenburg, B.; ten Holte, P. Top.
Curr. Chem. 2001, 216, 93–124; (d) Palacios, F.; Ochoa de
AcOEt); IR mmax (CHCl3): 3400, 3330, 1750 cmꢀ1 1H
;
NMR (300 MHz, CDCl3): 2.62 (br s, 2H, NH2), 3.74 (s,
3H, MeO), 3.76 (s, 3H, MeO), 5.72 (s, 1H), 7.29–7.38 (m,
7H, H(Ph)), 7.43–7.49 (m, 1H, H(Ph)), 7.88–7.91 (m, 2H,
H(Ph)); 13C NMR (75 MHz, CDCl3): 52.8 (MeO), 53.0
(MeO), 56.7 (CH), 69.8 (CN), 127.8, 128.1, 128.4, 128.5,
129.8, 132.7, 132.8, 135.8 C (Ph), 168.8 (C@O), 171.4
(C@O), 198.0 (C@O). Anal. Calcd for C19H19NO5: C,
66.85; H, 5.61; N, 4.10. Found: C, 66.53; H, 5.46; N, 4.13;
9a, mp 37–39 ꢁC (hexane); IR mmax (CHCl3): 1750 cmꢀ1; 1H
NMR (300 MHz, CDCl3): 2.39 (s, 3H, Me), 3.81 (s, 3H,
MeO), 4.55 (s, 1H, CH2@), 4.97 (s, 1H, CH2@), 7.17–7.20
(m, 2H, H(Ar)), 7.46–7.55 (m, 5H, H(Ar)), 7.91–7.93 (m,
2H, H(Ar)); 13C NMR (75 MHz, CDCl3): 20.9 (Me), 51.5
(MeO), 94.4 (CH2), 125.4, 127.8, 128.4, 128.7, 131.4,
133.1, 133.2, 138.1 (C(Ar)), 155.0 (C@), 158.4 (C@N),
164.9 (C@O). Anal. Calcd for C18H17NO2: C, 77.40; H,
6.13; N, 5.01. Found: C, 77.31; H, 6.35; N, 4.94; cis-10a,
ꢀꢀ
Retana, A. M.; Martynez de Marigorta, E.; de los Santos,
J. M. Eur. J. Org. Chem. 2001, 2401–2414; (e) Rai, K. M.
L.; Hassner, A. In Advances in Strained and Interesting
Organic molecules; Halton, B., Ed.; JAI: Stamford, 2000;
Vol. 8, pp 187–257.
7. Hassner, A.; Currie, J. O.; Steinfeld, A. S.; Atkinson, R. F.
J. Am. Chem. Soc. 1973, 95, 2982–2987.
8. Khlebnikov, A. F.; Novikov, M. S.; Amer, A. A.
Tetrahedron Lett. 2002, 43, 8523–8525.
9. (a) Nair, V. J. Org. Chem. 1968, 33, 2121–2123; (b) Nair,
V. J. Org. Chem. 1968, 33, 4316.
10. Komatsu, M.; Nishikaz, N.; Ohshiro, Y.; Agawa, T.
J. Org. Chem. 1976, 41, 3642–3643.
11. Data for selected compounds: 4a mp 95–97 ꢁC (hexane–
AcOEt); IR mmax (CHCl3): 1745 cmꢀ1; 1H NMR (300 MHz,
CDCl3): 3.88 (s, 3H, MeO), 6.14 (s, 1H,@CH), 7.10–7.16
(m, 5H, H(Ph)), 7.34–7.50 (m, 8H, H(Ph)), 7.87–7.90 (m,
2H, H(Ph)); 13C NMR (75 MHz, CDCl3): 51.6 (MeO),
113.2 (@CH), 126.2, 127.7, 127.9, 128.0, 128.3, 128.9,
129.1, 131.4, 133.2, 135.6, 135.9 C(Ph), 150.3 (@C), 157.6
(C@N), 165.2 (C@O). Anal. Calcd for C23H19NO2: C,
80.92; H, 5.61; N, 4.10. Found: C, 80.99; H, 5.75; N, 4.11;
4b mp 150 ꢁC (hexane); UV kmax/nm (log e) (hexane): 329
mp 156 ꢁC (hexane–CH2Cl2); IR mmax (CHCl3): 1735 cmꢀ1
;
1H NMR (300 MHz, CDCl3): 2.49 (s, 3H, Me), 3.74 (s,
3H, MeO), 3.89 (s, 3H, MeO), 3.91 (d, 1H, H4, J ¼ 17:4),
4.43 (d, 1H, H4, J ¼ 17:4), 6.77–6.80 (m, 2H, H(Ar)),
6.91–6.98 (m, 3H, H(Ar)), 7.03–7.06 (m, 3H, H(Ar)), 7.33–
7.41 (m, 4H, H(Ar)), 8.01–8.05 (m, 2H, H(Ar)); 13C NMR
(75 MHz, CDCl3): 21.3 (Me), 48.2 C4, 52.2 (MeO), 52.5
(MeO), 66.1 C3, 91.1 C2, 126.5, 126.6, 127.4, 127.9, 128.2,
129.1, 130.3, 137.3, 138.9, 141.9 C(Ar), 172.4, 173.8, 175.4
(2 C@O+C@N). Anal. Calcd for C27H25NO4: C, 75.86; H,
5.89; N, 3.28. Found: C, C, 75.82; H, 5.97; N, 3.21; trans-
10a, mp 159–160 ꢁC (hexane–CH2Cl2); IR mmax (CHCl3):
1
(4.18), 405 (3.79); IR mmax (CHCl3): 1750 cmꢀ1; H NMR
(300 MHz, CDCl3): 3.61 (br s, 3H, MeO), 6.65–6.68 (m,
1H, H(Ar)), 6.92–6.95 (m, 1H, H(Ar)), 7.22–7.27 (m, 2H,
H(Ar)), 7.35–7.38 (m, 1H, H(Ar)), 7.48–7.55 (m, 8H,
H(Ar)), 7.74–7.92 (m, 5H, H(Ar)); 13C NMR (75 MHz,
CDCl3): 51.86 (MeO), 118.9 C2, 119.1, 122.9, 123.4, 125.9,
126.1, 126.6, 126.7, 126.8, 128.1, 128.3, 128.5, 128.8, 129.8,
131.7, 133.5, 137.3, 137.4, 137.6, 139.1, 139.8 C(Ar), 147.6
(@CN), 159.3 (C@N), 164.4 (C@O). Anal. Calcd for
C29H21NO4: C, 83.83; H, 5.09; N, 3.37. Found: C, 83.92;
1750, 1740 cmꢀ1 1H NMR (300 MHz, CDCl3): 2.46 (s,
;
3H, Me), 3.30 (s, 3H, MeO), 3.55 (s, 3H, MeO), 3.56 (d,
1H, H4, J ¼ 16:7), 4.28 (d, 1H, H4, J ¼ 16:7), 7.26–7.36
(m, 10H, H(Ar)), 7.45–7.48 (m, 2H, H(Ar)), 7.96–7.99 (m,
2H, H(Ar)); 13C NMR (75 MHz, CDCl3): 21.2 (Me), 49.0
C(4), 51.7 (MeO), 51.9 (MeO), 67.7 C3, 91.4 C2, 125.9,
126.5, 126.6, 127.2, 127.8, 127.9, 128.0, 129.0, 130.3, 136.9,
141.8, 142.3 C(Ar), 170.1, 171.9, 173.8 (2 C@O, C@N).
Anal. Calcd for C27H25NO4: C, 75.86; H, 5.89; N, 3.28.
Found: C, 76.06; H, 6.03; N, 3.07.
1
H, 5.20; N, 3.37; 5, oil, IR mmax (CHCl3): 1750 cmꢀ1; H
NMR (300 MHz, CDCl3): 3.33 (s, 3H, MeO), 3.89 (s, 3H,
MeO), 5.44 (s, 1H, H(3)), 7.18–7.22 (m, 2H, H(Ph)), 7.27–