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M. Tiecco et al. / Tetrahedron: Asymmetry 18 (2007) 2758–2767
91 (11), 77(3); FT-IR (HATAR): 2091 cmꢀ1 (N3). Anal.
Calcd for C11H14N4: C, 65.32; H, 6.98; N, 27.70. Found:
C, 65.44; H, 6.86; N, 27.82.
References
1. (a) Lewis, J. R. Nat. Prod. Rep. 2001, 18, 95; (b) O’Hagan, D.
Nat. Prod. Rep. 2000, 17, 435; (c) Watson, P. S.; Jiang, B.;
Scott, B. Org. Lett. 2000, 2, 3679.
2. (a) Watson, A. A.; Fleet, G. W. J.; Asano, N.; Molyneux, R.
J.; Nash, R. J. Phytochemistry 2001, 56, 265; (b) Goti, A.;
Cicchi, S.; Mannucci, V.; Cardona, F.; Guarna, F.; Merino,
P.; Tejero, T. Org. Lett. 2003, 5, 4235.
4.10.2. (2S)-2-(Azidomethyl)-5-phenyl-3,4-dihydro-2H-pyr-
24
1
role, 21a0. Oil; ½aꢁD ¼ þ38:4 (c 0.69, CHCl3); H NMR:
d 7.87–7.84 (m, 2H), 7.48–7.40 (m, 3H), 4.51–4.42 (m,
1H), 3.63 (dd, 1H, J = 7.1, 12.4 Hz), 3.51 (dd, 1H,
J = 5.2, 12.3 Hz), 3.12 (dddd, 1H, J = 2.2, 4.9, 10.1,
12.3 Hz), 2.98 (dddd, 1H, J = 1.7, 7.3, 9.8, 12.3 Hz), 2.24
(dddd, 1H, J = 4.9, 8.1, 9.8, 13.5 Hz), 1.83 (dddd, 1H,
J = 7.3, 7.5, 10.1, 13.5 Hz); 13C NMR: d 174.5, 134.1,
130.7, 128.4 (two carbons), 127.8 (two carbons), 72.7,
55.7, 35.4, 25.9; MS m/z (rel int.): 200 (M+ <1%), 144
(100), 115 (44), 91 (58), 77 (20); FT-IR (HATAR):
2096 cmꢀ1 N3. Anal. Calcd for C11H12N4: C, 65.98; H,
6.04; N, 27.98. Found: C, 65.96; H, 6.12; N, 27.86.
3. (a) Dalko, P. I.; Moisan, L. Angew. Chem., Int. Ed. 2004, 43,
5138; (b) Shi, Y. Acc. Chem. Res. 2004, 37, 488.
4. (a) Kim, B. H.; Lee, H. B.; Hwang, J. K.; Kim, Y. G.
Tetrahedron: Asymmetry 2005, 16, 1215; (b) Sweet, J. A.;
Cavallari, J. M.; Price, W. A.; Ziller, J. W.; McGrath, D. V.
Tetrahedron: Asymmetry 1997, 8, 207; (c) Wang, Q.; Sasaki,
A. N.; Riche, C.; Potier, P. J. Org. Chem. 1999, 64, 8602.
5. (a) Davis, A. F.; Song, M.; Augustine, A. J. Org. Chem. 2006,
71, 2779, and references cited therein; (b) Shao, Z. H.; Peng,
F. Z.; Zhu, B. K.; Tu, Y. Q.; Zhang, H. B. Chin. J. Chem.
2004, 22, 727, and references cited therein; (c) Viso, A.; Lee,
N. E.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 9373; (d)
Yun, J.; Buchwald, S. L. Chirality 2000, 12, 476; (e) Wu, S.;
Lee, S.; Beak, P. J. Am. Chem. Soc. 1996, 118, 715.
6. Jones, A. D.; Redfern, A. L.; Knight, D. W.; Morgan, I. R.;
Williams, A. C. Tetrahedron 2006, 62, 9247, and references
cited therein.
7. (a) Clive, D. L. J.; Farina, V.; Singh, A.; Wong, C. K.; Kiel, W.
A.; Menchen, S. M. J. Org. Chem. 1980, 45, 2120; (b) Morella,
A. M.; Ward, A. D. Aust. J. Chem. 1995, 48, 445; (c) De Kimpe,
N.; Boelens, M. J. Chem. Soc., Chem. Commun. 1993, 916.
8. (a) Tiecco, M. Electrophilic Selenium, Selenocyclizations. In
Topics in Current Chemistry: Organoselenium Chemistry:
Modern Developments in Organic Synthesis; Wirth, T., Ed.;
Springer: Heidelberg, 2000; pp 7–54; (b) Organoselenium
Chemistry—A Pratical Approach; Back, T. G., Ed.; Oxford
University Press: New York, NY, 2000; (c) Wirth, T. Curr.
Org. Chem. 2006, 10, 1893.
4.10.3. [(2S,5S)-5-Phenylpyrrolidin-2-yl]acetonitrile, 21b.
25
1
Oil; ½aꢁD ¼ ꢀ20:3 (c 0.60, CHCl3); H NMR: d 7.37–7.24
(m, 5H), 4.40 (dd, 1H, J = 6.6, 7.0 Hz), 3.82 (quint, 1H,
J = 6.6 Hz), 2.55–2.51 (m, 2H), 2.39–2.21 (m, 2H), 1.99
(br s, 1H), 1.90–1.79 (m, 1H), 1.75–1.66 (m, 1H); 13C
NMR: d 144.2, 128.6 (two carbons), 127.2, 126.2 (two car-
bons), 118.5, 61.9, 54.6, 34.6, 31.8, 25.4; MS m/z (rel int.):
186 (5), 185 (17), 146 (100), 129 (49),117 (19), 104 (14), 91
(11); FT-IR (HATAR): 2246 cmꢀ1 CN. Anal. Calcd for
C12H14N2: C, 77.38; H, 7.58; N, 15.04. Found: C, 77.45;
H, 7.49; N, 15.18.
4.10.4.
[(2S)-5-Phenyl-3,4-dihydro-2H-pyrrol-2-yl]aceto-
1
nitrile, 21b0. Oil; slightly impure [a] not determined; H
NMR: d 7.86–7.84 (m, 2H), 7.50–7.39 (m, 3H), 4.55–4.45
(m, 1H), 3.20 (dddd, 1H, J = 2.2, 4.6, 10.1, 14.6 Hz), 3.02
(dddd, 1H, J = 1.8, 7.6, 9.5, 14.6 Hz), 2.84 (dd, 1H,
J = 5.1, 16.6 Hz), 2.77 (dd, 1H, J = 6.8, 16.7 Hz), 2.40
(dddd, 1H, J = 4.5, 7.9, 9.9, 12.6 Hz), 1.84 (dddd, 1H,
J = 6.8, 7.1, 10.0, 12.6 Hz); 13C NMR: d 174.5, 133.6,
131.0, 128.5 (two carbons), 127.8 (two carbons), 117.9,
68.5, 35.6, 27.9, 24.6. Anal. Calcd for C12H12N2: C,
78.23; H, 6.57; N, 15.21. Found: C, 78.35; H, 6.69; N,
15.33.
9. (a) Takada, H.; Nishibayashi, Y.; Uemura, S. J. Chem. Soc.,
Perkin Trans. 1 1999, 1511; (b) Nishibayashi, Y.; Srivastava,
S. K.; Takada, H.; Fukuzawa, S.; Uemura, S. J. Chem. Soc.,
Chem. Commun. 1995, 2321.
10. (a) Fragale, G.; Wirth, T. Eur. J. Org. Chem. 1998, 1361; (b)
Deziel, R.; Malefant, E. J. Org. Chem. 1995, 60, 4660; (c)
Back, T. G.; Dyck, B. P.; Nan, S. Tetrahedron 1999, 55, 3191.
11. (a) Tiecco, M.; Testaferri, L.; Marini, F.; Sternativo, S.;
Bagnoli, L.; Santi, C.; Temperini, A. Tetrahedron: Asymmetry
2001, 12, 1493; (b) Tiecco, M.; Testaferri, L.; Marini, F.;
Sternativo, S.; Santi, C.; Bagnoli, L.; Temperini, A. Tetrahe-
dron: Asymmetry 2001, 12, 3053; (c) Tiecco, M.; Testaferri,
L.; Bagnoli, L.; Purgatorio, V.; Temperini, A.; Marini, F.;
Santi, C. Tetrahedron: Asymmetry 2001, 12, 3297.
12. (a) Tiecco, M.; Testaferri, L.; Bagnoli, L.; Purgatorio, V.;
Temperini, A.; Marini, F.; Santi, C. Tetrahedron: Asymmetry
2004, 15, 405; (b) Tiecco, M.; Testaferri, L.; Bagnoli, L.;
Terlizzi, R.; Temperini, A.; Marini, F.; Santi, C.; Scarponi, C.
Tetrahedron: Asymmetry 2004, 15, 1949; (c) Tiecco, M.;
Testaferri, L.; Marini, F.; Sternativo, S.; Santi, C.; Bagnoli,
L.; Temperini, A. Tetrahedron: Asymmetry 2003, 14, 1095; (d)
Tiecco, M.; Testaferri, L.; Marini, F.; Sternativo, S.; Santi,
C.; Bagnoli, L.; Temperini, A. Tetrahedron: Asymmetry 2003,
14, 2651.
4.10.5. (2S,5S)-2-[(Methylthio)methyl]-5-phenylpyrrolidine,
28
21c. Oil; ½aꢁD ¼ þ26:6 (c 1.37, CHCl3); 1H NMR: d
7.40–7.20 (m, 5H), 4.30 (dd, 1H, J = 6.7, 7.0 Hz), 3.65
(quint, 1H, J = 6.7 Hz), 2.66–2.61 (m, 2H), 2.32–2.18 (m,
2H), 2.16 (s, 3H), 1.99 (br s, 1H), 1.84–1.74 (m, 1H),
1.68–1.57 (m, 1H); 13C NMR: d 145.1, 128.3 (two carbons),
126.8, 126.3 (two carbons), 60.9, 56.8, 40.9, 34.7, 31.5, 15.6;
MS m/z (rel int.): 207 (M <1%), 206 (1), 146 (100), 129 (78),
91 (11), 77 (8). Anal. Calcd for C12H17NS: C, 69.51; H,
8.26; N, 6.76. Found: C, 69.63; H, 8.37; N, 6.89.
13. Bernardi, L.; Bonini, B. F.; Comes-Franchini, M.; Fochi, M.;
Mazzanti, G.; Ricci, A.; Varchi, G. Eur. J. Org. Chem. 2002,
2776.
Acknowledgements
14. (a) Selenium Reagents and Intermediates in Organic Synthesis;
Paulmier, C., Ed.; Pergamon: Oxford, 1986; (b) Krief, A.;
Dumont, W.; Denis, J.-N.; Evrard, G.; Norberg, B. J. Chem.
Soc., Chem. Commun. 1985, 569; (c) Tiecco, M.; Testaferri,
Financial support from MIUR, National Projects
PRIN2003, PRIN2005, FIRB2001 and Consorzio CINM-
PIS is gratefully acknowledged.