K. Tanaka et al. / Tetrahedron 65 (2009) 9008–9014
9013
4.5.1. (4E)-2-Cyclohexyl-3-cyclohexylimino-4-pentylidene-3,4-
dihydro-2H-isoquinolin-1-one (3ga)
30.0, 26.6, 25.9, 25.8, 24.2, 21.1, 14.2; HRMS (ESI) calcd for
C
28H32N2ONa [MþNa]þ 435.2407, found 435.2412.
Yellow oil; IR (neat) 2928, 1854, 1673, 1637, 1357 cmꢀ1; 1H NMR
(CDCl3, 300 MHz)
d
8.16–8.09 (m, 1H), 7.51 (dt, J¼7.5, 1.5 Hz, 1H),
Acknowledgements
7.45–7.35 (m, 2H), 5.83 (t, J¼7.5 Hz, 1H), 4.64 (tt, J¼12.0, 3.6 Hz, 1H),
3.75 (tt, J¼8.4, 4.2 Hz, 1H), 2.55–2.33 (m, 2H), 2.42 (q, J¼7.5 Hz, 2H),
1.87–1.08 (m, 22H), 0.92 (t, J¼7.5 Hz, 3H); 13C NMR (CDCl3, 75 MHz)
This work was supported partly by a Grant-in-Aid for Scientific
Research (No. 20675002) from MEXT, Japan. We are grateful to
Umicore for generous supports in supply of a rhodium complex.
d
164.0, 151.3, 136.1, 133.3, 131.1, 128.8, 128.5, 127.8, 126.3, 126.0,
57.6, 55.8, 34.6, 31.8, 28.1, 26.6, 25.9, 25.8, 24.1, 22.4, 13.9; HRMS
(ESI) calcd for C26H37N2O [MþH]þ 393.2900, found 393.2932.
References and notes
1. For reviews of transition-metal-catalyzed cycloadditions, see: (a) Yet, L. Chem.
Rev. 2000, 100, 2963; (b) Wender, P. A.; Love, J. A. Advances in Cycloaddition; JAI:
Greenwich, 1999; Vol. 5; p 1; (c) Mehta, G.; Singh, V. Chem. Rev. 1999, 99, 881;
(d) Ojima, I.; Tzamarioudaki, M.; Li, Z.; Donovan, R. J. Chem. Rev. 1996, 96, 635;
(e) Lautens, M.; Klute, W.; Tam, W. Chem. Rev. 1996, 96, 49; (f) Schore, N. E.
Chem. Rev. 1988, 88, 1081.
2. For a review of cycloadditions through five-membered acylmetal intermediates
leading to six-membered carbonyl compounds, see: Tanaka, K. Chim. Oggi 2006,
24, 20.
4.5.2. (4E)-2-Isopropyl-3-isopropylimino-4-pentylidene-3,4-
dihydro-2H-isoquinolin-1-one (3gb)
Pale yellow oil; IR (neat) 2964, 2928, 1675, 1356, 1247 cmꢀ1; 1H
NMR (CDCl3, 300 MHz)
d
8.14 (dd, J¼7.5, 1.5 Hz, 1H), 7.51 (dt, J¼7.5,
1.5 Hz, 1H), 7.41 (dt, J¼7.5, 1.5 Hz, 1H), 7.40 (dd, J¼7.5, 1.5 Hz, 1H),
5.86 (t, J¼7.5 Hz, 1H), 5.05 (sept, J¼6.9, 1H), 4.06 (sept, J¼6.3, 1H),
2.43 (q, J¼7.5 Hz, 2H),1.57–1.43 (m, 2H),1.49 (d, J¼6.9 Hz, 6H),1.42–
1.25 (m, 2H), 1.16 (d, J¼6.3 Hz, 6H), 0.91 (t, J¼7.2 Hz, 3H); 13C NMR
3. For a review of rhodium-catalyzed [4þ2] cycloadditions, see: Robinson, J. E. In
Modern Rhodium-Catalyzed Organic Reactions; Evans, P. A., Ed.; Wiley-VCH:
Weinheim, 2005; p 241.
(CDCl3, 75 MHz) d 163.9, 151.3, 136.6, 133.3,131.2,128.8,128.4,127.8,
126.2, 126.1, 49.9, 47.2, 31.9, 28.2, 24.8, 22.4, 20.3, 13.9; HRMS (ESI)
4. (a) Reppe, W.; Vetter, H. Justus Liebigs Ann. Chem. 1953, 582, 133; (b) Maruyama,
K.; Shio, T.; Yamamoto, Y. Bull. Chem. Soc. Jpn. 1979, 52, 1877; (c) Foust, D. F.;
calcd for C20H29N2O [MþH]þ 313.2274, found 313.2267.
´
Rausch, M. D. J. Organomet. Chem. 1982, 239, 321; (d) Cabrera, A.; Mondragon, J.;
Torres, F.; Go´mez, L. J. Rev. Soc. Quim. Mex. 1983, 27, 311.
4.5.3. (4E)-4-Pentylidene-2-p-tolyl-3-p-tolylimino-
3,4-dihydro-2H-isoquinolin-1-one (3gc)
5. (a) Liebeskind, L. S.; Baysdon, S. L.; South, M. S. J. Am. Chem. Soc. 1980, 102, 7397;
(b) Baysdon, S. L.; Liebeskind, L. S. Organometallics 1982, 1, 771; (c) South, M. S.;
Liebeskind, L. S. J. Org. Chem. 1982, 47, 3815; (d) Liebeskind, L. S.; Baysdon, S. L.
Tetrahedron Lett. 1984, 25, 1747; (e) South, M. S.; Liebeskind, L. S. J. Am. Chem.
Soc. 1984, 106, 4181; (f) Liebeskind, L. S.; Leeds, J. P.; Baysdon, S. L.; Iyer, S. J. Am.
Chem. Soc. 1984, 106, 6451; (g) Liebeskind, L. S.; Baysdon, S. L.; South, M. S.; Iyer,
S.; Leeds, J. P. Tetrahedron 1985, 41, 5839; (h) Liebeskind, L. S.; Baysdon, S. L.;
Goedken, V.; Chidambaram, R. Organometallics 1986, 5, 1086; (i) Iyer, S.; Lie-
beskind, L. S. J. Am. Chem. Soc. 1987, 109, 2759; (j) Huffman, M. A.; Liebeskind, L.
S. J. Am. Chem. Soc. 1991, 113, 2771.
6. (a) Kondo, T.; Taguchi, Y.; Kaneko, Y.; Niimi, M.; Mitsudo, T. Angew. Chem., Int.
Ed. 2004, 43, 5369; (b) Kondo, T.; Niimi, M.; Nomura, M.; Wada, K.; Mitsudo, T.
Tetrahedron Lett. 2007, 48, 2837.
7. For the synthesis of five-membered rings by rhodium-catalyzed [3þ2] cyclo-
additions of cyclopropenones with alkynes, see: Wender, P. A.; Paxton, T. J.;
Williams, T. J. J. Am. Chem. Soc. 2006, 128, 14814.
8. (a) Murakami, M.; Itahashi, T.; Ito, Y. J. Am. Chem. Soc. 2002, 124, 13976; (b)
Matsuda, T.; Fujimoto, A.; Ishibashi, M.; Murakami, M. Chem. Lett. 2004, 33, 876.
9. For the synthesis of eight-membered rings from cyclobutanones, see: Wender,
P. A.; Correa, A. G.; Sato, Y.; Sun, R. J. Am. Chem. Soc. 2000, 122, 7815.
10. Tanaka, K.; Fu, G. C. Org. Lett. 2002, 4, 933.
11. (a) Tanaka, K.; Hagiwara, Y.; Noguchi, K. Angew. Chem., Int. Ed. 2005, 44, 7260;
(b) Tanaka, K.; Hagiwara, Y.; Hirano, M. Eur. J. Org. Chem. 2006, 3582.
12. Hojo, D.; Noguchi, K.; Hirano, M.; Tanaka, K. Angew. Chem., Int. Ed. 2008, 47, 5820.
13. Rhodium-catalyzed [4þ2] annulations of vinylarylaldehydes with alkenes and
alkynes leading to substituted tetralones and 1-naphthols were also reported; see:
(a) Tanaka, K.; Hojo, D.; Shoji, T.; Hagiwara, Y.; Hirano, M. Org. Lett. 2007, 9, 2059;
For a rhodium-catalyzed homo-[4þ2] annulation of vinylbenzaldehyde, see: (b)
Kundu, K.; McCullagh, J. V.; Morehead, A. T., Jr. J. Am. Chem. Soc. 2005, 127, 16042.
14. For reviews, see: (a) Heller, B.; Hapke, M. Chem. Soc. Rev. 2007, 36, 1085; (b)
Chopade, P. R.; Louie, J. Adv. Synth. Catal. 2006, 348, 2307; (c) Nakamura, I.;
Yamamoto, Y. Chem. Rev. 2004, 104, 2127; (d) Varela, J. A.; Saa`, C. Chem. Rev.
2003, 103, 3787.
15. (a) Hong, P.; Yamazaki, H. Synthesis 1977, 50; (b) Hong, P.; Yamazaki, H. Tetra-
hedron Lett. 1977, 1333; (c) Earl, R. A.; Vollhardt, K. P. C. J. Am. Chem. Soc. 1983,
105, 6991; (d) Earl, R. A.; Vollhardt, K. P. C. J. Org. Chem. 1984, 49, 4786; (e)
Diversi, P.; Ingrosso, G.; Lucherini, A.; Malquori, S. J. Mol. Catal. 1987, 40, 267; (f)
Bonaga, L. V. R.; Zhang, H.-C.; Gauthier, D. A.; Reddy, I.; Maryanoff, B. E. Org. Lett.
2003, 5, 4537; (g) Bonaga, L. V. R.; Zhang, H.-C.; Moretto, A. F.; Ye, H.; Gauthier,
D. A.; Li, J.; Leo, G. C.; Maryanoff, B. E. J. Am. Chem. Soc. 2005, 127, 3473.
16. (a) Hoberg, H.; Oster, B. W. Synthesis 1982, 324; (b) Hoberg, H.; Oster, B. W.
J. Organomet. Chem. 1982, 234, C35; (c) Hoberg, H.; Oster, B. W. J. Organomet.
Chem. 1983, 252, 359; (d) Duong, H. A.; Cross, M. J.; Louie, J. J. Am. Chem. Soc.
2004, 126, 11438; (e) Duong, H. A.; Louie, J. J. Organomet. Chem. 2005, 690,
5098; (f) Duong, H. A.; Louie, J. Tetrahedron 2006, 62, 7552.
Yellow solid; mp 115–116 ꢁC; IR (KBr) 2954, 2925, 2869, 1640,
1361 cmꢀ1; 1H NMR (CDCl3, 300 MHz)
d
8.23 (dd, J¼7.5, 1.5 Hz, 1H),
7.61 (dt, J¼7.5,1.5 Hz,1H), 7.50 (dt, J¼7.5,1.5 Hz,1H), 7.46 (d, J¼7.5 Hz,
1H), 7.36–7.17 (m, 4H), 7.07–6.96 (m, 2H), 6.67–6.55 (m, 2H), 6.00 (t,
J¼7.8 Hz,1H), 2.40 (s, 3H), 2.27 (s, 3H), 2.23 (q, J¼7.8 Hz, 2H),1.30–1.16
(m, 2H), 1.16–1.01 (m, 2H), 0.80 (t, J¼7.2 Hz, 3H); 13C NMR (CDCl3)
d
164.5,146.3,143.8,137.4,135.2,133.5,132.2,132.1,129.7,129.4,128.7,
128.6, 128.1, 127.9, 126.2, 122.5, 120.9, 31.1, 28.4, 22.0, 21.2, 20.7, 13.8;
HRMS (ESI) calcd for C28H29N2O [MþH]þ 409.2274, found 409.2274.
4.5.4. (4E)-2-Cyclohexyl-3-cyclohexylimino-4-cyclohexyl-
methylene-3,4-dihydro-2H-isoquinolin-1-one (3ha)
Colorless solid; mp 142–143 ꢁC; IR (KBr) 2926, 2853, 1675, 1638,
1344 cmꢀ1; 1H NMR (CDCl3, 300 MHz)
d
8.13 (dd, J¼7.5, 1.2 Hz, 1H),
7.51 (dt, J¼7.5, 1.5 Hz, 1H), 7.41 (dt, J¼7.5, 1.2 Hz, 1H), 7.37 (d, J¼7.5,
1H), 5.65 (d, J¼10.5 Hz, 1H), 4.63 (tt, J¼12.0, 3.3 Hz, 1H), 3.72 (tt,
J¼8.4, 4.2 Hz, 1H), 2.68–2.52 (m, 1H), 2.44 (dq, J¼12.0, 3.3 Hz, 2H),
1.92–0.88 (m, 28H); 13C NMR (CDCl3, 75 MHz)
d 164.1, 151.6, 141.3,
133.5, 131.3, 128.9, 128.5, 127.8, 125.6, 124.1, 60.4, 57.8, 55.7, 36.7,
34.7, 32.9, 26.6, 25.9, 25.8, 25.7, 25.2, 24.2, 21.0, 14.2; HRMS (ESI)
calcd for C28H39N2O [MþH]þ 419.3057, found 419.3064.
4.5.5. (4E)-2-Cyclohexyl-3-cyclohexylimino-4-trimethylsilanyl-
methylene-3,4-dihydro-2H-isoquinolin-1-one (3ia)
Pale yellow solid; mp 125–126 ꢁC; IR (KBr) 2928, 2852, 1638,
1216, 1096 cmꢀ1 1H NMR (CDCl3, 300 MHz)
; d 8.11–8.04 (m, 1H),
7.52–7.40 (m, 3H), 5.85 (s, 1H), 4.60 (tt, J¼12.6, 3.3 Hz, 1H), 3.72 (tt,
J¼8.4, 4.2 Hz, 1H), 2.42 (dq, J¼12.6, 3.3 Hz, 2H), 1.98–1.00 (m, 18H),
0.13 (s, 9H); 13C NMR (CDCl3, 75 MHz)
d 164.0, 152.3, 141.4, 135.9,
135.4, 131.0, 128.9, 128.7, 128.2, 125.4, 57.7, 55.9, 34.5, 29.8, 26.6,
25.9, 25.8, 24.0, 0.2; HRMS (ESI) calcd for C25H37N2OSi [MþH]þ
409.2670, found 409.2685.
17. (a) Yamamoto, Y.; Takagishi, H.; Itoh, K. Org. Lett. 2001, 3, 2117; (b) Yamamoto,
Y.; Kinpara, K.; Saigoku, T.; Takagishi, H.; Okuda, S.; Nishiyama, H.; Itoh, K. J. Am.
Chem. Soc. 2005, 127, 605.
4.5.6. (4E)-4-Benzylidene-2-cyclohexyl-3-cyclohexylimino-3,4-
dihydro-2H-isoquinolin-1-one (3ja)
18. For cationic rhodium(I)/biaryl bisphosphine complex-catalyzed [2þ2þ2] cy-
cloadditions of alkynes with isocyanates, see: (a) Tanaka, K.; Wada, A.; Noguchi,
K. Org. Lett. 2005, 7, 4737; (b) Tanaka, K.; Takahashi, Y.; Suda, T.; Hirano, M.
Synlett 2008, 1724; For neutral rhodium(I) complex-catalyzed [2þ2þ2] cyclo-
additions of alkynes with isocyanates, see: (c) Flynn, S. T.; Hasso-Henderson, S.
E.; Parkins, A. W. J. Mol. Catal. 1985, 32, 101; (d) Yu, R. T.; Rovis, T. J. Am. Chem.
Soc. 2006, 128, 2782; (e) Kondo, T.; Nomura, M.; Ura, Y.; Wada, K.; Mitsudo, T.
Tetrahedron Lett. 2006, 47, 7107; (f) Yu, R. T.; Rovis, T. J. Am. Chem. Soc. 2006, 128,
Colorless solid; mp 65–66 ꢁC; IR (KBr) 2928, 2852, 1674, 1638,
1344 cmꢀ1; 1H NMR (CDCl3, 300 MHz)
d
8.11 (d, J¼7.8 Hz, 1H), 7.39–
7.32 (m, 1H), 7.30–7.17 (m, 7H), 6.72 (s, 1H), 4.66 (tt, J¼12.3, 3.0 Hz,
1H), 3.98 (tt, J¼8.4, 4.2, 1H), 2.46 (dq, J¼12.3, 3.0 Hz, 2H), 1.94–1.19
(m, 18H); 13C NMR (CDCl3)
d 164.1, 150.8, 134.9, 132.6, 132.0, 130.8,
129.2, 128.54, 128.51, 128.4, 128.3, 126.9, 126.6, 60.4, 58.1, 56.0, 34.7,