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D. Kawai et al. / Tetrahedron 65 (2009) 10390–10394
5.7. 1,1-Dicyano-6,6-dimethyl-2-phenylspiro[2.5]-
octane-4,8-dione (3eb)
5.12. Triethyl 2-cyano-3-phenyl-1,1,2-cyclopropane-
tricarboxylate13 (3ag)
Colorless plates; Mp 77–78 ꢀC (EtOH); IR (KBr) 3597, 3406,
2968, 2874, 2249, 1702, 1447, 1375, 1309, 1224, 1046, 737, 698; 1H
1H NMR (200 MHz, CDCl3)
d 1.06–1.42 (m, 9H), 3.93 (s, 1Htrans),
4.01 (s, 1Hcis), 4.08–4.41 (m, 6H), 7.27–7.40 (m, 5H).
NMR (200 MHz, CDCl3)
(s, 2H), 4.12 (s, 1H), 7.1–7.2 (m, 2H), 7.3–7.4 (m, 3H); 13C NMR
(50 MHz, CDCl3) 22.1, 28.5, 29.0, 30.2, 44.3, 49.4, 53.2, 54.4, 109.5,
111.0, 127.1, 128.4, 128.8, 128.9, 195.9, 198.0; Anal. Calcd for
C18H18N4O2þ1/2$EtOH: C, 72.36, H, 6.07, N, 8.88. Found: C, 72.03,
H, 6.23, N, 8.82.
d 1.21 (s, 6H), 2.68 (s, 1H), 2.71 (s, 1H), 2.83
5.13. Ethyl 1,2,2-tricyano-3-ethylcyclopropanecarboxyl-ate
(3ah)
d
1H NMR (200 MHz, CDCl3)
d
1.15 (t, J¼7.3 Hz, 3Htrans), 1.25 (t,
J¼7.3 Hz, 3Hcis), 1.38–1.45 (m, 3H), 1.87–2.04 (m, 2H), 2.70 (t,
J¼7.5 Hz, 1Htrans), 2.79 (t, J¼7.5 Hz, 1Hcis), 4.36–4.49 (m, 2H).
5.8. 1,1-Dicyano-N,N-dimethyl-2-phenyl-5,7-diazaspiro-
[2.5]octane-4,6,8-trione (3fb)
Acknowledgements
Colorless plates; Mp 219–220 ꢀC (EtOH); IR (KBr) 3065, 2244,
This work was partially supported by a Grant-in-Aid for Scien-
tific Research (No. 14340195) from the Ministry of Education, Sci-
ence, Sport and Culture, Japan.
1676, 1595, 1449, 1311, 1254, 1180, 1020, 938, 802, 763, 695, 595,
1
546; H NMR (200 MHz, CDCl3)
d 3.33 (s, 3H), 3.49 (s, 3H), 4.30 (s,
1H), 7.24–7.34 (m, 2H), 7.38–7.46 (m, 3H); 13C NMR (50 MHz, CDCl3)
23.0, 29.7, 30.1, 40.9, 45.1, 108.8, 110.4, 126.1, 128.3, 129.0, 129.4,
d
References and notes
149.5, 158.6, 161.3; Anal. Calcd for C16H12N4O3: C, 62.33; H, 3.92; N,
18.17. Found: C, 62.00; H, 3.71; N, 17.87.
1. (a) Wessjohann, L. A.; Thiemann, W. B. Chem. Rev. 2003, 103, 1625–1648;
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5.9. TBABr mediated reactions of 1a with alkenes 2 (Table 4)
To a mixture of 1a (154 mg, 1.0 mmol) and TBABr (322 mg,
1.0 mmol) in THF (1 mL), 2c (100 mg, 0.50 mmol) was added, and
the mixture was stirred for 5 h. The product was extracted with
Et2O, washed with H2O and brine, and dried over Na2SO4. The sol-
vent was evaporated, and the product was purified by chromato-
graphy on SiO2 (hexane–EtOAc¼2:1, then EtOAc) affording
cyclopropane 3ac (67 mg, 43%, dr¼81:19).
5.10. Diethyl 1,2-dicyano-3-phenyl-1,2-
cyclopropanedicarboxylate9 (3ac)
1H NMR (200 MHz, CDCl3)
J¼7.2 Hz, 6Hcis), 1.44 (t, J¼7.1 Hz, 3Htrans), 3.93, (s, 1Hcis), 4.11 (s,
1Htrans), 4.18 (dq, J¼2.9, 7.1 Hz, 2Htrans), 4.34 (q, J¼7.2 Hz, 4Hcis),
4.42–4.51 (m, 2Htrans), 7.36 (s, 5Hcis), 7.42–7.47 (m, 5Htrans).
d
1.15 (t, J¼7.1 Hz, 3Htrans), 1.36 (t,
5.11. Diethyldicyanofumarate12 (4)
12. Boul, P. J.; Reutenauer, P.; Lehn, J. Org. Lett. 2005, 7, 15–18.
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P. A.; Nikishin, G. I. Tetrahedron 2006, 62, 3989–3996.
1H NMR (200 MHz, CDCl3)
J¼7.2 Hz, 6HE), 4.46 (q, J¼7.2 Hz, 4HZ), 4.52 (q, J¼7.2 Hz, 4HE).
d
1.42 (t, J¼7.2 Hz, 6HZ), 1.46 (t,