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J. Feng et al. / Tetrahedron 63 (2007) 6035–6041
2H), 6.95 (dd, J¼2.1 Hz, 6.6 Hz, 2H), 6.53 (d, J¼2.1 Hz,
1H), 4.35–4.27 (m, 2H), 3.83 (s, 3H), 3.78 (d, J¼7.5 Hz,
1H), 3.55–3.53 (m, 1H), 1.81–1.63 (m, 2H), 1.36 (t,
J¼7.2 Hz, 3H), 1.28–1.16 (m, 2H), 0.84 (t, J¼7.2 Hz, 3H).
13C NMR (75 MHz, CDCl3): d 162.6, 160.1, 147.4, 130.2,
129.5, 126.5, 114.4, 114.4, 111.8, 61.6, 59.8, 55.2, 48.6,
45.6, 33.3, 19.5, 14.0. IR (oil): n 2963, 2936, 2249, 1724,
1516, 1257 cmꢂ1. MS (m/z) 339 (M++1), 338, 309, 295,
121, 43 (100). HRMSEI: Calcd for C20H23N2O3 (M++1):
339.1703. Found: 339.1709.
1242 cmꢂ1. MS (m/z) 333 (M++1), 332, 89, 43 (100).
HRMSEI: Calcd for C20H16N2O3Na+ (M++Na): 355.1053.
Found: 355.1060. The stereochemistry was further deter-
mined by NOESY spectra (see Supplementary data).
3.3.2.8. (cis)-1-Ethoxycarbonyl-3,3-dicyano-4-phenyl-
5-(a-furyl)cyclopentene (9f0). Oil. 1H NMR (300 MHz,
CDCl3) d 7.64–7.61 (m, 2H), 7.54 (d, J¼1.8 Hz, 1H),
7.48–7.43 (m, 3H), 6.58 (d, J¼3.0 Hz, 1H), 6.51 (d, J¼
2.4 Hz, 1H), 6.46 (dd, J¼2.1 Hz, 3.3 Hz, 1H), 4.70 (d,
J¼9.0 Hz, 1H), 4.36 (dd, J¼2.4 Hz, 9.6 Hz, 1H), 4.25 (q, J¼
6.9 Hz, 2H), 1.30 (t, J¼7.2 Hz, 3H). 13C NMR (75 MHz,
CDCl3): d 161.7, 149.8, 144.5, 142.4, 132.7, 131.4, 129.5,
129.2, 128.2, 113.5, 111.3, 110.6, 108.1, 61.6, 60.5, 47.3,
45.0, 13.8. IR (oil): n 2986, 2251, 1727, 1242 cmꢂ1. MS
(m/z) 333 (M++1), 332, 89, 43 (100). HRMSEI: Calcd for
C20H16N2O3Na+ (M++Na): 355.1053. Found: 355.1057.
The stereochemistry was further determined by NOESY
spectra (see Supplementary data).
3.3.2.4.
(trans)-1-Ethoxycarbonyl-3,3-dicyano-4-
phenyl-5-i-butylcyclopentene (9d). Oil. 1H NMR
(300 MHz, CDCl3) d 7.46–7.35 (m, 5H), 6.52 (d, J¼
1.8 Hz, 1H), 4.32 (qd, J¼2.1 Hz, 7.2 Hz, 2H), 3.81 (d, J¼
6.0 Hz, 1H), 3.60–3.53 (m, 1H), 1.83–1.76 (m, 1H), 1.56–
1.44 (m, 2H), 1.38 (t, J¼7.2 Hz, 3H), 0.86 (d, J¼6.6 Hz,
3H), 0.74 (d, J¼6.6 Hz, 3H). 13C NMR (75 MHz, CDCl3):
d 162.5, 148.5, 135.8, 129.7, 129.4, 129.2, 128.1, 114.5,
111.8, 61.7, 61.1, 48.3, 45.8, 42.5, 25.8, 23.4, 21.4, 14.1.
IR (oil): n 3091, 2961, 2250, 1725, 1638, 1371 cmꢂ1
.
Acknowledgements
MS (EI): m/z: 322 (M+), 293, 234, 193, 166, 84
(100). HRMS: Calcd for C20H22N2O2: 322.1681. Found:
322.1684.
We thank the National Natural Sciences Foundation of
China (20572121) and Chinese Academy of Sciences for
financial support.
3.3.2.5.
(trans)-1-Ethoxycarbonyl-3,3-dicyano-4-
phenyl-5-(p-nitrophenyl)cyclopentene (9e). Oil; 1H
NMR (300 MHz, CDCl3) d 8.18–8.13 (m, 2H), 7.45 (s,
5H), 7.31–7.27 (m, 2H), 6.89 (d, J¼2.1 Hz, 1H), 4.82 (dd,
J¼9.6 Hz, 2.1 Hz, 1H), 4.22–4.10 (m, 2H), 3.96 (d, J¼
9.6 Hz, 1H), 1.17 (t, J¼7.2 Hz, 3H). 13C NMR (75 MHz,
CDCl3): d 161.5, 147.4, 145.8, 145.4, 132.7, 131.2, 130.0,
129.4, 128.5, 128.2, 124.1, 113.3, 111.1, 64.2, 61.9, 53.4,
Supplementary data
Experimental procedure, characterization data, copies of
1H and 13C NMR spectra for new compounds, and NOESY
spectra of compounds 9a, 9e, 9e0, 9f, and 9f0 are provided.
Supplementary data associated with this article can be
45.6, 13.8. IR (oil): n 3083, 2985, 2251, 1726, 1682 cmꢂ1
.
MS (EI): m/z: 387 (M+), 359, 288 (100), 268, 191. HRMS:
Calcd for C22H17N3O4: 387.1219. Found: 387.1218. The
stereochemistry was further determined by NOESY spectra
(see Supplementary data).
References and notes
1. For reviews on phosphine-catalyzed reactions, see: (a)
Methot, J. L.; Roush, W. R. Adv. Synth. Catal. 2004, 346,
1035; (b) Lu, X.; Zhang, C.; Xu, Z. Acc. Chem. Res. 2001,
34, 535.
2. For recent reports on phosphine-catalyzed reactions, see: (a)
Wilson, J. E.; Fu, G. C. Angew. Chem., Int. Ed. 2006, 45,
1426; (b) Zhao, G.-L.; Shi, M. Org. Biomol. Chem. 2005,
3, 3686; (c) Zhu, X.-F.; Henry, C. E.; Wang, J.; Dudding,
T.; Kwon, O. Org. Lett. 2005, 7, 1387; (d) Yavari, I.;
Souri, S.; Sirouspour, M.; Djahaniani, H.; Nasiri, F.
3.3.2.6. (cis)-1-Ethoxycarbonyl-3,3-dicyano-4-phenyl-
5-(p-nitrophenyl)cyclopentene (9e0). Oil. 1H NMR
(300 MHz, CDCl3): d 8.38–8.35 (m, 2H), 7.78–7.74 (m,
2H), 7.64–7.61 (m, 2H), 7.50–7.47 (m, 3H), 6.59 (d, J¼
2.4 Hz, 1H), 4.65 (d, J¼9.6 Hz, 1H), 4.38 (dd, J¼2.4 Hz,
9.6 Hz, 1H), 4.21 (q, J¼7.2 Hz, 2H), 1.26 (t, J¼7.2 Hz,
3H). 13C NMR (75 MHz, CDCl3): d 169.0, 148.6, 139.9,
138.4, 130.6, 130.3, 129.8, 129.3, 126.4, 124.4, 113.8,
112.3, 62.5, 57.5, 52.9, 47.5, 14.1. IR (oil): n 3114, 3085,
2985, 2249, 1737, 1684 cmꢂ1. MS (EI): m/z: 387 (M+), 386,
314, 288 (100), 268, 191. HRMS: Calcd for C22H17N3O4:
387.1219. Found: 387.1220. The stereochemistry was fur-
ther determined by NOESY spectra (see Supplementary
data).
ꢀ
Synthesis 2005, 1761; (e) Hanedanian, M.; Loreau, O.;
Sawicki, M.; Taran, F. Tetrahedron 2005, 61, 2287; (f)
Zhu, X.-F.; Henry, C. E.; Kwon, O. Tetrahedron 2005, 61,
6276; (g) Yong, S. R.; Williams, M. C.; Pyne, S. G.; Ung,
A. T.; Skelton, B. W.; White, A. H.; Turner, P.
Tetrahedron 2005, 61, 8120; (h) Virieux, D.; Guillouzic,
A.-F.; Cristau, H.-J. Tetrahedron 2006, 62, 3710; (i)
ꢀ
3.3.2.7.
(trans)-1-Ethoxycarbonyl-3,3-dicyano-4-
Hanedanian, M.; Loreau, O.; Taran, F.; Mioskowski, C.
phenyl-5-(a-furyl)cyclopentene (9f). Oil. 1H NMR
(300 MHz, CDCl3) d 7.45 (s, 5H), 7.33 (d, J¼1.2 Hz,
1H), 6.76 (d, J¼2.1 Hz, 1H), 6.28 (dd, J¼2.4 Hz, 3.6 Hz, 1H),
6.17 (d, J¼2.7 Hz, 1H), 4.81 (dd, J¼9.0 Hz, 2.4 Hz, 1H),
4.29–4.12 (m, 3H), 1.26 (t, J¼7.2 Hz, 3H). 13C NMR
(75 MHz, CDCl3): d 161.7, 149.8, 144.5, 142.4, 132.7,
131.4, 129.5, 129.2, 128.2, 113.5, 111.3, 110.6, 108.1,
61.6, 60.5, 47.3, 45.0, 13.8. IR (oil): n 2986, 2251, 1727,
Tetrahedron Lett. 2004, 45, 7035; (j) Jean, L.; Marinetti,
A. Tetrahedron Lett. 2006, 47, 2141.
3. (a) Du, Y.; Lu, X.; Zhang, C. Angew. Chem., Int. Ed. 2003, 42,
1035; (b) Du, Y.; Feng, J.; Lu, X. Org. Lett. 2005, 7, 1987.
4. Lu, Z.; Lu, X.; Zhang, X. Tetrahedron 2006, 62, 457.
5. For the use of 5a as the electrophilic olefin in [3+2] annulation
reactions, see: Boivin, J.; Tailhan, C.; Zard, S. Z. J. Am. Chem.
Soc. 1991, 113, 5874.