R. Ballini et al. / Tetrahedron 59 (2003) 3603–3608
3607
50.2, 53.4, 60.0, 62.5. MS m/z (%): 199 (Mþ, 9), 198 (15),
184 (100), 140 (12), 100 (39), 71 (34), 58 (31), 43 (37), 44
(37), 32 (44). Anal. calcd for C12H25NO (199.33) C, 72.31;
H, 12.64; N, 7.03. Found C, 72.29; H, 12.61; N, 7.00.
References
1. Review (a) Mitchinson, A.; Nadin, A. J. Chem. Soc. Perkin
`
Trans. 1 2000, 2862–2892. (b) Pinchon, M.; Figadere, B.
Tetrahedron: Asymmetry 1996, 7, 927–964.
4.3.9. 1-Ethyl-3-(1-methylethyl)pyrrolidine, 8i. Yield
1
2. For some recent examples see: (a) Verma, S. K.; Atanes, M. N.;
Busto, J. H.; Thai, D. L.; Rapoport, H. J. Org. Chem. 2002, 67,
1314–1318. (b) Schlummer, B.; Hartwig, J. F. Org. Lett. 2002,
4, 1471–1474. (c) Palacios, F.; Alonso, C.; Amezua, P.;
Rubiales, G. J. Org. Chem. 2002, 67, 1941–1946. (d) Smith,
S. C.; Bentley, P. D. Tetrahedron Lett. 2002, 43, 899–902.
70%; oil; H NMR d (ppm) 1.00 (d, 6H, J¼6.2 Hz), 1.11
(t, 3H, J¼7.3 Hz), 1.50–1.75 (m, 2H), 1.87–2.06 (m, 1H),
2.08–2.23 (m, 1H), 2.30–2.58 (m, 4H), 2.65–2.92 (m, 2H).
13C NMR d (ppm) 12.2, 18.6, 20.6, 26.8, 31.1, 32.1, 48.0,
53.3, 59.8. MS m/z (%): 141 (Mþ, 20), 140 (20), 126 (100),
83 (12), 71 (18), 55 (11), 42 (11), 29 (4). Anal. calcd for
C9H19N (141.25) C, 76.53; H, 13.56; N, 9.92. Found C,
76.59; H, 13.59; N, 9.89.
¨
(e) Karlsson, S.; Hogberg, H.-E. Tetrahedron: Asymmetry
2001, 712, 1977–1982.
3. (a) Krow, G. R.; Yuan, J.; Lin, G.; Sonnet, P. E. Org. Lett.
2002, 4, 1259–1262. (b) Greenwood, E. S.; Parsons, P. J.
Synlett 2002, 167–169. (c) Li, Z.; Feiten, H.-J-; Chang, D.;
Duetz, W. A.; van Beilen, J. B.; Witholt, B. J. Org. Chem.
2001, 66, 8424–8430.
4.3.10. 3-Cyclohexyl-1-ethylpyrrolidine, 8j. Yield 85%;
oil; 1H NMR d (ppm) 1.07 (t, 3H, J¼7.3 Hz), 1.55–1.95 (m,
14H), 1.99–2.10 (m, 1H), 2.20–2.52 (m, 3H), 2.70–2.86
(m, 2H). 13C NMR d (ppm) 13.6, 26.2, 28.6, 30.0, 31.7,
32.0, 44.9, 50.5, 53.6, 58.4, 61.8. MS m/z (%): 181 (Mþ, 17),
180 (16), 166 (100), 98 (5), 81 (13), 71 (20), 58 (17), 41
(10). Anal. calcd for C12H23N (181.32) C, 79.49; H, 12.79;
N, 7.72. Found C, 79.45; H, 12.82; N, 7.75.
4. Reviews: (a) Speckamp, W. N.; Moolenaar, M. J. Tetrahedron
2000, 56, 3817–3856. (b) De Koning, H.; Speckamp, W. N.
Stereoselective Synthesis (Houben-Weyl); Helmchen, G.,
Hoffman, R. W., Mulzer, J., Schaumann, E., Eds.; Georg
Thieme: Stuttgart, 1995; Vol. E21, pp 1953–2009.
5. (a) Enders, D.; Teschner, P.; Raabe, G.; Runsink, J. Eur.
J. Org. Chem. 2001, 4463–4477. (b) Zhang, X.; Jang, W.;
Schmitt, A. C. Tetrahedron Lett. 2001, 42, 4943–4945.
(c) Hitchcock, P. B.; Starkmann, B. A.; Young, D. W.
Tetrahedron Lett. 2001, 42, 2381–2384. (d) Cossy, J.;
Tresnard, L.; Belotti, D.; Gomez Pardo, D. Tetrahedron Lett.
2001, 42, 251–254.
4.3.11. 3-Ethyl-1-phenylpyrrolidine, 8k. Yield 85%; oil;
1H NMR d (ppm) 0.98 (t, 3H, J¼7.5 Hz), 1.42–1.70 (m,
3H), 2.09–2.28 (m, 2H), 2.86–2.92 (m, 1H), 3.22–3.47 (m,
3H), 6.50–6.68 (m, 3H), 7.18–7.27 (m, 2H). 13C NMR d
(ppm) 12.8, 26.8, 31.4, 40.6, 47.5, 53.3, 111.4, 115.27,
129.12, 148.0. MS m/z (%): 175 (Mþ, 68), 174 (68), 144 (9),
119 (33), 104 (30), 91 (100), 77 (44), 51 (13), 41 (9). Anal.
calcd for C12H17N (175.27) C, 82.23; H, 9.78; N, 7.99.
Found C, 82.18; H, 9.82; N, 8.03.
¨
6. Chihab-Eddine, A.; Daıch, A.; Jilale, A.; Decroix, B.
Tetrahedron Lett. 2001, 42, 573–576.
7. (a) Curran, D. P.; Geib, S.; De Mello, N. Tetrahedron 1999,
55, 5681–5704. (b) Mikami, T.; Harada, M.; Narasaka, K.
Chem. Lett. 1999, 425–426. (c) Gutemberger, G.; Steckhan,
E.; Blechert, S. Angew. Chem. Int. Ed. 1998, 37, 660–662.
(d) Meggers, E.; Steckhan, E.; Blechert, S. Angew. Chem. Int.
Ed. 1995, 34, 2137–2139.
4.3.12. 3-Butyl-1-phenylpyrrolidine, 8l.19 Yield 79%; oil;
1H NMR d (ppm) 0.92 (t, 3H, J¼6.2 Hz), 1.25–1.58 (m,
4H), 1.62–1.97 (m, 3H), 2.12–2.40 (m, 2H), 2.90–3.06
(m, 1H), 3.33–3.60 (m, 3H), 6.50–6.68 (m, 3H), 7.18–7.27
(m, 2H). 13C NMR d (ppm) 14.0, 22.5, 29.9, 30.4, 34.6,
44.3, 47.5, 54.3, 111.5, 115.4, 129.1, 148.0. MS m/z (%):
203 (Mþ, 88), 202 (72), 144 (16), 119 (38), 106 (57), 91
(100), 77 (42), 55 (12), 41 (12), 29 (10). Anal. calcd for
C14H21N (203.32) C, 82.70; H, 10.41; N, 6.89. Found C,
82.65; H, 10.38; N, 6.86.
8. Cunningham, I. D.; Brownhill, A.; Hamerton, I.; Howlin, B.
Tetrahedron 1997, 53, 13473–13494.
9. (a) Ono, N. The Nitro Group in Organic Synthesis; Wiley-
VCH: New York, 2001. (b) Perlmutter, P. Conjugate
Addition Reactions in Organic Synthesis; Pergamon: Oxford,
1992.
10. (a) Ballini, R.; Bosica, G. Tetrahedron 1995, 51, 4213–4222.
(b) Ballini, R.; Bosica, G. Liebigs Ann. 1996, 2087–2089.
11. Ballini, R.; Barboni, L.; Bosica, G.; Petrini, M. Synlett 2000,
391–393.
4.3.13. 3-(1-Methylethyl)-1-phenylpyrrolidine, 8m. Yield
77%; waxy solid; 1H NMR d (ppm) 1.00 (d, 6H, J¼6.2 Hz),
1.50–1.75 (m, 2H), 1.87–2.06 (m, 1H), 2.08–2.23 (m, 1H),
2.90–3.00 (m, 1H), 3.22–3.50 (m, 3H), 6.50–6.68 (m, 3H),
7.18–7.27 (m, 2H). 13C NMR d (ppm) 21.4, 21.8, 30.5,
32.7, 46.7, 48.1, 52.5, 112.5, 115.4, 129.3, 148.1. MS m/z
(%): 189 (Mþ, 67), 188 (56), 146 (12), 119 (36), 104 (31),
91 (100), 77 (46), 51 (11), 41 (16). Anal. calcd for C13H19N
(189.30) C, 82.48; H, 10.12; N, 7.40. Found C, 82.51; H,
10.08; N, 7.38.
12. Ballini, R.; Bosica, G.; Fiorini, D.; Giarlo, G. Synthesis 2001,
2003–2006.
13. Ballini, R.; Bosica, G.; Fiorini, D.; Gil, M. V.; Petrini, M. Org.
Lett. 2001, 3, 1265–1267.
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14. Ballini, R.; Bosica Mase, A.; Petrini, M. Eur. J. Org. Chem.
2000, 2927–2931.
15. Katritzky, A. R.; Yao, J.; Qi, M.; Chou, Y.; Sikora, D. J.;
Davis, S. Hetrocycles 1998, 48, 2677–2691.
16. (a) Ballini, R.; Bosica, G. Synlett 1996, 1115–1116. For a
review on this reducing couple see: (b) Ganem, B.; Osby, J. O.
Chem. Rev. 1986, 86, 763–780.
Acknowledgements
Financial support from University of Camerino and
17. (a) Tsuzuki, Y.; Chiba, K.; Hino, K. Tetrahedron: Asymmetry
2001, 12, 1793–1799. (b) Zhang, H. K.; Chen, Q. F.; Huang,
P. Q. Synth. Commun. 2000, 30, 2431–2444. (c) Rao, V. D.;
Perisamy, M. Synthesis 2000, 703–706. (d) Kuwano, R.;
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MIUR (National Project ‘Sintesi e Reattivita–attivita di
Sistemi Insaturi Funzionalizzati’) is gratefully
acknowledged.