N. Hasegawa et al. / Tetrahedron 69 (2013) 4466e4472
4471
(m, 1H). 13C NMR (100.53 MHz, CDCl3):
d
15.68, 15.79, 33.05, 33.11,
129.10, 129.65, 129.95, 130.00, 135.99, 136.08, 136.52, 136.57, 149.02,
149.04, 156.52, 156.81, 175.27, 175.41, 181.89, 182.07. IR (neat): 1776
m, 1709 s, 1589 m, 1495 m, 1456 m, 1435 m, 1390 s, 1362 s, 1255 w,
1188 m, 1153 m, 1124 w, 1078 w, 997 w, 912 m, 791 w, 733 m, 702 s,
633 w, 611 w, 586 w. MS, m/z (relative intensity, %): 370 (Mþ, 2.9),
168 (20), 167 (100), 91 (19), 79 (29). HRMS: calcd for C24H22N2O2:
370.1681. Found: 370.1682.
36.31, 36.37, 40.93, 41.00, 50.95, 51.03,120.65,120.75,122.17,122.19,
126.96, 128.74, 129.13, 129.23, 136.41, 136.43, 137.01, 137.11, 149.12,
158.03, 176.10, 179.04. IR (neat): 1774 m, 1703 s, 1590 w, 1541 w,
1495 w, 1473 w, 1437 w, 1392 s, 1363 m, 1290 w, 1228 w, 1194 m,
1155 w, 1111 w, 1036 w, 995 w, 960 w, 920 w, 883 w, 802 w, 775 w,
750 m, 704 m, 607 w. MS, m/z (relative intensity, %): 295 (11), 294
(Mþ, 53), 293 (26), 203 (19), 121 (15), 117 (26), 115 (15),107 (61), 106
(100), 91 (40), 79 (26), 78 (22), 65 (12), 55 (11). HRMS: calcd for
C18H18N2O2: 294.1368. Found: 294.1366.
Acknowledgements
This work was supported, in part, by a Grant-in-Aid for Scientific
Research on Innovative Areas ‘Molecular Activation Directed to-
ward Straightforward Synthesis’ from The Ministry of Education,
Culture, Sports, Science and Technology.
4.3.3. 3-(1-(Pyridin-2-yl)ethyl)-3-azabicyclo[3.1.0]hexane-2,4-dione
(2u). White solid. Mp: 65.5 ꢀC. Rf¼0.17 (Hexane/EtOAc¼1/1). 1H
NMR (400 MHz, CDCl3): d 1.47e1.52 (m, 1H), 1.64e1.67 (m, 1H), 1.77
(d, J¼7.6, 3H), 2.43e2.51 (m, 2H), 5.25 (q, J¼7.2, 1H), 7.15 (dd, J¼4.8,
7.2, 1H), 7.32 (d, J¼8.0, 1H), 7.66 (dt, J¼1.6, 8.0, 1H), 8.50 (d, J¼5.2,
References and notes
1H). 13C NMR (100 MHz, CDCl3):
d 16.09, 19.95, 20.09, 20.16, 49.92,
120.54, 122.14, 136.44, 149.07, 158.26, 175.03, 175.12. IR (KBr): 1772
w, 1705 s, 1591 w, 1572 w, 1473 w, 1435 w, 1387 m, 1356 m, 1188 w,
1043 w, 997 w, 949 w, 908 w, 858 w, 827 w, 804 w, 781 w, 764 w,
642 w, 609 w. MS, m/z (relative intensity, %): 216 (Mþ, 41), 147 (12),
121 (45), 120 (18), 119 (10), 107 (10), 106 (100), 105 (16), 104 (14), 95
(13), 93 (15), 79 (37), 78 (34), 70 (10), 68 (24), 55 (10), 52 (14), 51 (2).
1. For reviews on carbonylation, see: Colquhoun, H. M.; Thompson, D. J.; Twigg,
M. V. Carbonylation: Direct Synthesis of Carbonyl Compounds; Plenum: New York,
NY, 1991.
2. For recent reviews on functionalization of CeH bonds, see: (a) Kakiuchi, F.;
Kochi, T. Synthesis 2008, 3013; (b) Colby, D. A.; Bergman, R. G.; Ellman, J. A.
Chem. Rev. 2010, 110, 624; (c) Sehnal, P.; Taylor, R. J. K.; Fairlamb, I. J. S. Chem.
Rev. 2010, 110, 824; (d) Lyons, T. W.; Sanford, M. S. Chem. Rev. 2010, 110, 1147; (e)
Xu, L.-M.; Li, B.-J.; Yang, Z.; Shi, Z.-J. Chem. Soc. Rev. 2010, 39, 712; (f)
Ackermann, L. Chem. Commun. 2010, 4866; (g) Ackermann, L. Chem. Rev. 2011,
111, 1315; (h) Chen, D. Y.-K.; Youn, S. W. Chem.dEur. J. 2012, 18, 9452.
3. Murahashi, S. J. Am. Chem. Soc. 1955, 77, 6403.
4.3.4. 3-(1-(Pyridin-2-yl)ethyl)-3-azabicyclo[3.2.0]heptane-2,4-
dione (2v). Pale brown oil. Rf¼0.37 (EtOAc). 1H NMR (399.78 MHz,
4. For papers on the Pd-catalyzed carbonylation of CeH bonds, see: (a)
Orito, K.; Horibata, A.; Nakamura, T.; Ushito, H.; Nagasaki, H.; Yuguchi, M.; Ya-
mashita, S.; Tokuda, M. J. Am. Chem. Soc. 2004, 126, 14342; (b) Orito, K.; Miya-
zawa, M.; Nakamura, T.; Horibata, A.; Ushito, H.; Nagasaki, H.; Yuguchi, M.;
Yamashita, S.; Yamazaki, T.; Tokuda, M. J. Org. Chem. 2006, 71, 5951; (c) Giri, R.;
Yu, J.-Q. J. Am. Chem. Soc. 2008, 130, 14082; (d) Houlden, C. E.; Hutchby, M.;
CDCl3):
d
1.87 (d, J¼7.2 Hz, 3H), 2.16e2.32 (m, 2H), 2.58e2.72 (m,
2H), 3.26e3.32 (m, 2H), 5.52 (q, J¼7.2 Hz,1H), 7.17 (dd, J¼8.0, 4.0 Hz,
1H), 7.39 (d, J¼8.0 Hz, 1H), 7.68 (td, J¼8.0, 1.6 Hz, 1H), 8.53 (d,
J¼4.4 Hz, 1H). 13C NMR (100.53 MHz, CDCl3):
d 15.71, 22.92, 23.12,
ꢀ
Bailey, C. D.; Ford, J. G.; Tyler, S. N. G.; Gagne, M. R.; Lloyd-Jones, G. C.; Booker-
38.14, 38.21, 50.62, 120.59, 122.12, 136.45, 149.10, 158.28, 179.75,
179.83. IR (ATR): 2989 w, 2948 w, 2361 w, 2340 w, 1767 w, 1692 s,
1591 w, 1572 w, 1472 w, 1435 w, 1379 m, 1357 m, 1296 w, 1242 w,
1183 m, 1119 w, 1089 w, 1034 w, 992 w, 957 w, 927 w, 868 w, 801 w,
784 w, 762 w, 747 w. MS, m/z (relative intensity, %): 230 (Mþ, 47),
121 (25), 107 (11), 106 (100), 105 (17), 93 (13), 79 (29), 78 (23), 70
(10), 55 (14), 54 (14), 53 (16), 51 (11). HRMS: calcd for C13H14N2O2:
230.1055. Found: 230.1057.
Milburn, K. I. Angew. Chem., Int. Ed. 2009, 48,1830; (e) Giri, R.; Lam, J. K.; Yu, J.-Q. J.
Am. Chem. Soc. 2010, 132, 686; (f) Li, H.; Cai, G.-X.; Shi, Z.-J. Dalton Trans. 2010, 39,
10442; (g) Yoo, E. J.; Wasa, M.; Yu, J.-Q. J. Am. Chem. Soc. 2010, 132, 17378; (h)
Haffemayer, B.; Gulias, M.; Gaunt, M. J. Chem. Sci. 2011, 2, 312; (i) Lu, Y.; Leow, D.;
ꢀ
Wang, X.; Engle, K. M.; Yu, J.-Q. Chem. Sci. 2011, 2, 967; (j) Lopez, B.; Rodriguez,
A.; Santos, D.; Albert, J.; Ariza, X.; Garcia, J.; Granell, J. Chem. Commun. 2011,1054;
(k) Wrigglesworth, J. W.; Cox, B.; Lloyd-Jones, G. C.; Booker-Milburn, K. I. Org.
Lett. 2011, 13, 5326; (l) Ma, B.; Wang, Y.; Peng, J.; Zhu, Q. J. Org. Chem. 2011, 76,
6362; (m) Zhang, H.; Liu, D.; Chen, C.; Liu, C.; Lei, A. Chem.dEur. J. 2011, 17, 9581;
(n) Lang, R.; Shi, L.; Li, D.; Xia, C.; Li, F. Org. Lett. 2012, 14, 4130; (o) Zhang, H.; Shi,
R.; Gan, P.; Liu, C.; Ding, A.; Wang, Q.; Lei, A. Angew. Chem., Int. Ed. 2012, 51, 5204;
(p) Guan, Z.-H.; Chen, M.; Ren, Z.-H. J. Am. Chem. Soc. 2012, 134, 17490; (q) Liang,
D.; Hu, Z.; Peng, J.; Huang, J.; Zhu, Q. Chem. Commun. 2012, 173.
4.3.5. 3-Benzyl-3-methyl-1-(1-(pyridin-2-yl)ethyl)pyrrolidine-2,5-
dione (18). Colorless oil. Rf¼0.23 (Hexane/EtOAc¼1/1). 1H NMR
5. For papers on the Rh-catalyzed carbonylation of C(sp2)eH bonds, see: Guan, Z.-
H.; Ren, Z.-H.; Spinella, S. M.; Yu, S.; Liang, Y.-M.; Zhang, X. J. Am. Chem. Soc.
2009, 131, 729; Du, Y.; Hyster, T. K.; Rovis, T. Chem. Commun. 2011, 12074; Lang,
R.; Wu, J.; Shi, L.; Xia, C.; Li, F. Chem. Commun. 2011, 12553.
(399.78 MHz, CDCl3):
d
1.39e1.43 (s, 3H), 1.61e1.69 (d, J¼7.4 Hz,
3H), 2.34e2.43 (d, J¼18.4 Hz, 1H), 2.68 (d, J¼13.2 Hz, 1H), 2.77e2.80
(d, J¼18.4 Hz, 1H), 3.19e3.20 (d, J¼13.2 Hz, 1H), 5.30e5.38 (q,
J¼7.4 Hz, 1H), 6.98e7.19 (m, 4H), 7.24e7.26 (m, 3H), 7.55e7.61 (t,
J¼7.6 Hz, 1H), 8.48, 8.50 (d, J¼4.4 Hz, 1H). 13C NMR (100.53 MHz,
6. For papers on the Ru-catalyzed carbonylation of C(sp2)eH bonds, see: (a)
Moore, E. J.; Pretzer, W. R.; O’Connell, T. J.; Harris, J.; LaBounty, L.; Chou, L.;
Grimmer, S. S. J. Am. Chem. Soc. 1992, 114, 5888; (b) Chatani, N.; Fukuyama, T.;
Kakiuchi, F.; Murai, S. J. Am. Chem. Soc. 1996, 118, 493; (c) Chatani, N.; Ie, Y.;
Kakiuchi, F.; Murai, S. J. Org. Chem. 1997, 62, 2604; (d) Fukuyama, T.; Chatani, N.;
Kakiuchi, F.; Murai, S. J. Org. Chem. 1997, 62, 5647; (e) Ishii, Y.; Chatani, N.;
Kakiuchi, F.; Murai, S. Organometallics 1997, 16, 3615; (f) Ishii, Y.; Chatani, N.;
Kakiuchi, F.; Murai, S. Tetrahedron Lett. 1997, 38, 7565; (g) Fukuyama, T.;
Chatani, N.; Tatsumi, J.; Kakiuchi, F.; Murai, S. J. Am. Chem. Soc. 1998, 120, 11522;
(h) Chatani, N.; Ishii, Y.; Ie, Y.; Kakiuchi, F.; Murai, S. J. Org. Chem. 1998, 63, 5129;
(i) Ie, Y.; Chatani, N.; Ogo, T.; Marshall, D. R.; Fukuyama, T.; Kakiuchi, F.; Murai,
S. J. Org. Chem. 2000, 65, 1475; (j) Chatani, N.; Fukuyama, T.; Tatamidani, H.;
Kakiuchi, F.; Murai, S. J. Org. Chem. 2000, 65, 4039; (k) Chatani, N.; Asaumi, T.;
Ikeda, T.; Yorimitsu, S.; Ishii, Y.; Kakiuchi, F.; Murai, S. J. Am. Chem. Soc. 2000,
122, 12882; (l) Szewczyk, J. W.; Zuckerman, R. L.; Bergman, R. G.; Ellman, J. A.
Angew. Chem., Int. Ed. 2001, 40, 216; (m) Chatani, N.; Yorimitsu, S.; Asaumi, T.;
Kakiuchi, F.; Murai, S. J. Org. Chem. 2002, 67, 7557; (n) Asaumi, T.; Chatani, N.;
Matsuo, T.; Kakiuchi, F.; Murai, S. J. Org. Chem. 2003, 68, 7538; (o) Asaumi, T.;
Matsuo, T.; Fukuyama, T.; Ie, Y.; Kakiuchi, F.;Chatani, N. J. Org. Chem. 2004, 69, 4433;
(p) Chatani, N.; Uemura, T.; Asaumi, T.; Ie, Y.; Kakiuchi, F.; Murai, S. Can. J. Chem.
2005, 83, 755; (q) Imoto, S.; Uemura, T.; Kakiuchi, F.; Chatani, N. Synlett 2007, 170.
7. Sakakura, T.; Sodeyama, K.; Sasaki, K.; Wada, K.; Tanaka, M. J. Am. Chem. Soc.
1990, 112, 7221.
CDCl3): d 15.40,15.64, 25.43, 39.35, 39.45, 43.22, 43.25, 44.58, 44.74,
50.76, 50.83, 120.32, 120.61, 121.98, 122.04, 127.05, 128.49, 128.52,
129.92, 130.04, 136.07, 136.29, 148.92, 149.01, 157.98, 158.03, 175.38,
175.45, 181.95, 182.02. IR (neat): 1774 m, 1701 s, 1591 m, 1574 w,
1495 w, 1471 m, 1454 m, 1437 m, 1394 s, 1363 s, 1288 w, 1255 w,
1228 w,1198 s,1153 w,1095 w,1074 w,1030 w, 995 w, 957 w, 916 w,
864 w, 800 w, 768 m, 748 m, 706 m, 602 w. MS, m/z (relative in-
tensity, %): 308 (Mþ, 28), 307 (16), 294 (17), 293 (77), 217 (12), 117
(27), 115 (12), 107 (23), 106 (100), 91 (81), 79 (20), 78 (19), 69 (10),
65 (12). HRMS: calcd for C19H20N2O2: 308.1525. Found: 308.1523.
4.3.6. 3-Benzyl-3-methyl-1-(phenyl(pyridin-2-yl)methyl)pyrroli-
dine-2,5-dione (20). Colorless oil. Rf¼0.31 (Hexane/EtOAc¼1/1). 1H
NMR (399.78 MHz, CDCl3):
d 1.41 1.43 (s, 3H), 2.38e2.42 (d,
J¼18.0 Hz, 1H), 2.67e2.69 (d, J¼13.6 Hz, 1H), 2.79e2.80 (d,
J¼18.0 Hz, 1H), 3.19e3.20 (d, J¼13.2 Hz, 1H), 6.45e6.47 (s, 1H),
6.89e7.06 (m, 3H), 7.13e7.31 (m, 9H), 7.51e7.56 (m, 1H), 8.50e8.54
8. For recent reviews on functionalization of C(sp3)eH bond, see: Jazzar, R.; Hitce,
J.; Renaudat, A.; Sofack-Kreutzer, J.; Baudoin, O. Chem.dEur. J. 2010, 16, 2654;
Baudoin, O. Chem. Soc. Rev. 2011, 40, 4902.
9. Shiota, H.; Ano, Y.; Aihara, Y.; Fukumoto, Y.; Chatani, N. J. Am. Chem. Soc. 2011,
133, 14952.
(m, 1H). 13C NMR (100.53 MHz, CDCl3):
d 25.48, 25.54, 39.33, 39.43,
42.95, 43.10, 44.74, 44.84, 59.50, 59.74, 122.04, 122.14, 122.41,
122.85, 126.89, 126.95, 127.94, 128.09, 128.39, 128.44, 128.48,
10. Inoue, S.; Shiota, H.; Fukumoto, Y.; Chatani, N. J. Am. Chem. Soc. 2009, 131, 6898.