M. Schuler et al. / Tetrahedron: Asymmetry 21 (2010) 1569–1573
1573
4.2.9. Cyclohexyl 4,4-dicyano-5-(thiophen-2-yl)cyclo-pent-1-
4.2.13. Diethyl 1-cyano-2-phenylcyclopent-3-ene-1,3-
dicarboxylate 7a
ene-1-carboxylate 3h0
Yield: 80%. Yellow solid (mp 76–77 °C). Rf 0.49 (heptane/AcOEt
70/30). 1H NMR (300 MHz, CDCl3) d (ppm): 7.35–7.30 (m, 1H),
7.08–7.05 (m, 2H), 6.96–6.92 (m, 1H), 5.09–5.06 (br s, 1H), 4.85–
4.75 (m, 1H), 3.47 (dt, J = 18.3; 2.1 Hz, 1H), 3.38 (dd, J = 18.3;
3.0 Hz, 1H), 1.83–1.21 (m, 10H). 13C NMR (75 MHz, CDCl3) d
(ppm): 161.3 (C), 138.4 (C), 137.8 (CH), 136.5 (C), 128.1 (CH),
127.9 (CH), 126.8 (CH), 116.5 (C), 113.1 (C), 73.8 (CH), 55.1 (CH),
43.2 (CH2), 40.5 (C), 31.4 (CH2), 31.1 (CH2), 25.3 (CH2), 23.3
Yield: 67%. Colorless oil. Rf 0.43 (Hept/AcOEt 70/30). 1H NMR
(500 MHz, CDCl3) d: 7.38–7.27 (m, 3H), 7.19 (d, J = 7.0 Hz, 2H),
6.89 (br s, 1H), 4.70 (br s, 1H), 4.37–4.27 (m, 2H), 4.12–3.98 (m,
2H), 3.40 (dd, 2J = 18.5 Hz, 3J = 2.7 Hz, 1H), 3.19 (dt, 2J = 18.5;
3J = 4J = 2.4 Hz, 1H), 1.35 (t, J = 7.2 Hz, 3H), 1.09 (t, J = 7.3 Hz, 3H).
13C NMR (125 MHz, CDCl3) d: 168.4 (C), 163.1 (C), 148.4 (C),
139.9 (CH), 136.9 (C), 129.0 (CH), 128.7 (CH), 128.2 (CH), 117.8
(C), 63.8 (CH2), 60.9 (CH2), 58.7 (CH), 53.6 (C), 42.3 (CH2), 14.2
(CH2), 23.1 (CH2). IR (neat) (
m
, cmꢁ1): 715, 726, 791, 934, 979,
(CH3), 14.1 (CH3). IR (neat) (
1260, 1331, 1710, 1742, 2247, 2982. HRMS (ESI+) m/z: calcd for
18H19NNaO4 [M+Na]+: 336.1212; found: 336.1222. HPLC (Chir-
m
, cmꢁ1): 699, 1023, 1055, 1240,
1007, 1101, 1198, 1257, 1271, 1322, 1428, 1451, 1636, 1709,
2252, 2857, 2944. HRMS (ESI+) m/z: calcd for C18H18N2O2NaS
[M+Na]+: 349.0987; found: 349.0999. HPLC (Chiracel IC, heptane/
EtOH 98/2, 1 mL/min): tr (minor) = 20.1 min; tr (major) = 21.2 min.
C
alpak IC, heptane/EtOH 95/5, 1mL/min): tr (major) = 13.6 min; tr
(major) = 15.7 min (47% ee).
½
a 2D5
ꢀ
¼ þ155 (c 1.06, CHCl3, 88% ee).
Acknowledgments
4.2.10. Ethyl 4,4-dicyano-5-(pyridin-2-yl)cyclopent-1-ene-1-
carboxylate 3i13
Authors warmly thank the Agence Nationale de la Recherche
(ANR) for financial support to M.S. and the COST PhoSciNet Action
for supporting research on phosphine organocatalysis.
Yield: 77%. Orange oil. Rf 0.21 (heptane/AcOEt 50/50). 1H NMR
(500 MHz, CDCl3) d: 8.64 (d, J = 5.0 Hz, 1H), 8.51 (s, 1H), 7.53 (d,
J = 8.0 Hz, 1H), 7.35 (dd, J = 8.0; 5.0 Hz, 1H), 7.00 (br s, 1H), 4.79
(br s, 1H), 4.17–4.04 (m, 2H), 3.46 (br d, J = 18.3 Hz, 1H), 3.40 (br
d, J = 18.3 Hz, 1H), 1.14 (t, J = 7.2 Hz, 3H). HRMS (ESI+) m/z: calcd
for C15H14N3O2 [M+H]+: 268.1086; found: 268.1086. HPLC (Chir-
alpak IC, heptane/EtOH 85/15, 1 mL/min): tr (major) = 17.9 min; tr
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4.2.11. Ethyl 4,4-dicyano-5-(quinolin-2-yl)cyclopent-1-ene-1-
carboxylate 3j
Yield: 86%. Orange solid (mp 103–105 °C). Rf 0.23 (heptane/
AcOEt 70/30). 1H NMR (300 MHz, CDCl3) d: 8.17 (d, J = 8.4 Hz,
1H), 7.97 (br d, J = 8.7 Hz, 1H), 7.79 (br d, J = 8.1 Hz, 1H), 7.68
(ddd, J = 8.5; 7.0; 1.4 Hz, 1H), 7.52 (ddd, J = 8.1; 7.0; 1.1 Hz, 1H),
7.45 (d, J = 8.4 Hz, 1H), 6.97–6.94 (m, 1H), 4.96 (br s, 1H), 4.18–
4.02 (m, 2H), 3.97 (dt, J = 17.7; 3.0 Hz, 1H), 3.44 (dd, J = 17.7,
3.0 Hz, 1H), 1.16 (t, J = 7.1 Hz, 3H). 13C NMR (75 MHz, CDCl3) d:
162.5 (C), 155.3 (C), 148.1 (C), 138.9 (CH), 137.7 (C), 137.4 (CH),
130.1 (CH), 129.7 (CH), 128.0 (C), 127.9 (CH), 127.3 (CH), 121.4
(CH), 117.2 (C), 113.8 (C), 61.4 (CH2), 61.2 (CH), 45.2 (CH2), 39.2
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2005, 70, 6369–6377.
(C), 14.2 (CH3). IR (neat) (m
, cmꢁ1): 724, 752, 784, 809, 834, 919,
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cyclization processes. See: (a) Feng, J.; Lu, X.; Kong, A.; Han, X. Tetrahedron
2007, 63, 6035–6041; (b) Tran, Y. S.; Kwon, O. J. Am. Chem. Soc. 2007, 129,
12632–12633; (c) Lu, Z.; Zheng, S.; Zhang, X.; Lu, X. Org. Lett. 2008, 10, 3267–
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990, 1009, 1027, 1099, 1206, 1244, 1338, 1371, 1418, 1503,
1592, 1635, 1699, 2255, 2924. HRMS (ESI+) m/z: calcd for
C
19H16N3O2 [M+H]+: 318.1243; found: 318.1245. HPLC (Chiralpak
IA, heptane/iPrOH 95/5, 1 mL/min): tr (minor) = 16.0 min; tr (ma-
jor) = 19.3 min. ½a D25
¼ þ44 (c 1.05, CHCl3, 28% ee).
ꢀ
4.2.12. Ethyl 4,4-dicyano-5-(1-methyl-1H-indol-2-yl)cyclopent-
1-ene-1-carboxylate 3k
14. Guan, X.-Y.; Shi, M. J. Org. Chem. 2009, 74, 1977–1981.
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T.; Dingerdissen, U.; Beller, M. Tetrahedron Lett. 2002, 43, 4977–4980.
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Yield: 77%. White solid (mp 161–162 °C). Rf 0.28 (heptane/AcOEt
70/30). 1H NMR (300 MHz, CDCl3) d: 7.52 (dm, J = 7.8 Hz, 1H), 7.34
(dd, J = 8.1; 0.6 Hz, 1H), 7.27–7.20 (m, 1H), 7.09 (ddd, J = 8.0; 7.1;
1.1 Hz, 1H), 6.96–6.93 (m, 1H), 6.30 (br s, 1H), 5.07 (s, 1H), 4.21–
4.05 (m, 2H), 3.88 (s, 3H), 3.48 (dt, J = 18.0; 2.1 Hz, 1H), 3.35 (dd,
J = 18.0; 3.0 Hz, 1H), 1.19 (t, J = 7.1 Hz, 3H). 13C NMR (75 MHz, CDCl3)
d: 161.9 (C), 138.8 (C), 137.8 (CH), 136.7 (C), 131.5 (C), 127.1 (C),
122.9 (CH), 121.1 (CH), 120.3 (CH), 116.6 (C), 113.1 (C), 109.9 (CH),
102.0 (CH), 61.7 (CH2), 52.1 (CH), 43.4 (CH2), 38.7 (C), 30.4 (CH3),
18. Selected NMR data: 1H NMR (CDCl3, 300 MHz) d: 7.2 (1H, CH=), 4.2 (m, 1H,
3
CHPh, partly hidden under the OCH2 signals), 3.08 (ddd, JAB = 18.4 Hz, JH-
3
3
H = 9.6 Hz, JH-H = 2.1 Hz, 1H), 2.93 (ddd, JAB = 18.4 Hz, 7.8 Hz, JH-H = 3.0 Hz,
1H); 13C NMR (125 MHz, CDCl3) d: 115.7 (C), 63.3 (OCH2), 61.5 (OCH2), 59.8 (C),
55.6 (CHPh), 37.2 (CH2), 14.2 (Me) ppm The 1H NMR pattern of the CH2 moiety
of 7b as well as the chemical shifts of the C(CN)(CO2Et), CHPh, and CH2 carbons
in the 13C NMR spectra enables structural assignment.
19. (a) Corson, B. B.; Stoughton, R. W. J. Am. Chem. Soc. 1928, 50, 2825–2837; (b)
Oh, H.; Yang, J. H.; Lee, H. W.; Lee, I. J. Org. Chem. 2000, 65, 2188–2191; (c)
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Eur. J. Org. Chem. 2004, 546–551.
20. (a) Junge, K.; Hagemann, B.; Enthaler, S.; Spannenberg, A.; Michalik, M.;
Oehme, G.; Monsees, A.; Riermeier, T.; Beller, M. Tetrahedron: Asymmetry 2004,
15, 2621–2631; (b) Enthaler, S.; Erre, G.; Junge, K.; Holz, J.; Börner, A.; Alberico,
E.; Nieddu, I.; Gladiali, S.; Beller, M. Org. Process Res. Dev. 2007, 11, 568–577.
14.2 (CH3). IR (neat) (m
, cmꢁ1): 900, 997, 1022, 1091, 1170, 1203,
1249, 1320, 1339, 1465, 1631, 1704, 2359, 2927. HRMS (ESI+) m/z:
calcd for C19H18N3O2 [M+H]+: 320.1399; found: 320.1413. HPLC
(Chiralpak IA, heptane/iPrOH 98/2, 1 mL/min): tr (minor) = 27.9 -
min; tr (major) = 30.0 min. ½a D25
¼ þ272 (c 0.87, CHCl3, 99% ee (after
ꢀ
crystallization in CHCl3).