ORGANIC
LETTERS
2007
Vol. 9, No. 18
3519-3521
N-Heterocyclic Carbene Catalyzed Ring
Expansion of 4-Formyl- -lactams:
Synthesis of Succinimide Derivatives
â
Gong-Qiang Li, Yi Li, Li-Xin Dai, and Shu-Li You*
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic
Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, China
Received June 8, 2007
ABSTRACT
N-Heterocyclic carbene (NHC) has been employed as an efficient catalyst for ring expansion of 4-formyl-â-lactams, allowing the facile synthesis
of succinimide derivatives. This organocatalytic process features readily availability of the catalyst, low catalyst loading, and mild reaction
conditions.
Reversing the reactivity of aldehydes, also known as reactiv-
ity Umpolung,1 by N-heterocyclic carbene (NHC) has
become an intense research area recently.2 This approach
generally includes the reaction of the Breslow intermediate
with various acceptors such as aromatic aldehydes (Benzoin
reaction3), R,â-unsaturated systems (Stetter reaction4), ke-
tones,5 aziridines,6 and imines.7 The extended Umpolung
reactions involving the use of R,â-unsaturated aledehydes
or R-haloaldehydes have also received great attention and
witnessed significant progress in the past several years.8-10
It was recently reported by Bode and co-workers that formyl-
substituted epoxides, aziridines, and cyclopropanes under-
went the ring opening during the redox esterifications.11 Ring
opening of 4-formyl-â-lactams triggered by 2-(trimethylsi-
lyl)thiazole and ring expansion of 4-imino-â-lactam catalyzed
(5) (a) Hachisu, Y.; Bode, J. W.; Suzuki, K. J. Am. Chem. Soc. 2003,
125, 8432. (b) Hachisu, Y.; Bode, J. W.; Suzuki, K. AdV. Synth. Catal.
2004, 346, 1097. (c) Enders, D.; Niemeier, O.; Balensiefer, T. Angew.
Chem., Int. Ed. 2006, 45, 1463. (d) Takikawa, H.; Hachisu, Y.; Bode, J.
W.; Suzuki, K. Angew. Chem., Int. Ed. 2006, 45, 3492. (e) Enders, D.;
Niemeier, O.; Raabe, G. Synlett 2006, 2431.
(1) (a) Grobel, B. T.; Seebach, D. Synthesis 1977, 357. (b) Seebach, D.
Angew. Chem., Int. Ed. 1979, 18, 239.
(2) For reviews on NHC as organic catalysts: (a) Enders, D.; Balensiefer,
T. Acc. Chem. Res. 2004, 37, 534. (b) Johnson, J. S. Angew. Chem., Int.
Ed. 2004, 43, 1326. (c) Zeitler, K. Angew. Chem., Int. Ed. 2005, 44, 7506.
(d) Marion, N.; D´ıez-Gonza´lez, S.; Nolan, S. P. Angew. Chem., Int. Ed.
2007, 46, 2988.
(6) Liu, Y.-K.; Li, R.; Yue, L.; Li, B.-J.; Chen, Y.-C.; Wu, Y.; Ding,
L.-S. Org. Lett. 2006, 8, 1521.
(3) (a) Breslow, R. J. Am. Chem. Soc. 1958, 80, 3719. (b) Sheehan, J.;
Hunneman, D. H. J. Am. Chem. Soc. 1966, 88, 3666. (c) Enders, D.;
Kallfass, U. Angew. Chem., Int. Ed. 2002, 41, 1743. (d) Tachibana, Y.;
Kihara, N.; Takata, T. J. Am. Chem. Soc. 2004, 126, 3438.
(7) Li, G.-Q.; Dai, L.-X.; You, S.-L. Chem. Commun. 2007, 852 and
references cited therein.
(8) R,â-Unsaturated aldehydes: (a) Burstein, C.; Glorius, F. Angew.
Chem., Int. Ed. 2004, 43, 6025. (b) Sohn, S. S.; Rosen, E. L.; Bode, J. W.
J. Am. Chem. Soc. 2004, 126, 14370. (c) Chan, A.; Scheidt, K. A. Org.
Lett. 2005, 7, 905. (d) He, M.; Bode, J. W. Org. Lett. 2005, 7, 3131. (e)
Sohn, S. S.; Bode, J. W. Org. Lett. 2005, 7, 3873. (f) Zeitler, K. Org. Lett.
2006, 8, 637. (g) Nair, V.; Vellalath, S.; Poonoth, M.; Mohan, R.; Suresh,
E. Org. Lett. 2006, 8, 507.
(9) R-Haloaldehydes: (a) Reynolds, N. T.; Read de Alaniz, J.; Rovis,
T. J. Am. Chem. Soc. 2004, 126, 9518. (b) Reynolds, N. T.; Rovis, T. J.
Am. Chem. Soc. 2005, 127, 16406. (c) He, M.; Uc, G. J.; Bode, J. W. J.
Am. Chem. Soc. 2006, 128, 15088.
(4) (a) Stetter, H. Angew. Chem., Int. Ed. 1976, 15, 639. (b) Kerr, M.
S.; Read de Alaniz, J.; Rovis, T. J. Am. Chem. Soc. 2002, 124, 10298. (c)
Kerr, M. S.; Rovis, T. Synlett 2003, 1934. (d) Pesch, J.; Harms, K.; Bach,
T. Eur. J. Org. Chem. 2004, 2025. (e) Mattson, A. E.; Bharadwaj, A. R.;
Scheidt, K. A. J. Am. Chem. Soc. 2004, 126, 2314. (f) Kerr, M. S.; Rovis,
T. J. Am. Chem. Soc. 2004, 126, 8876. (g) Mennen, S. M.; Blank, J. T.;
Tran-Dube´, M. B.; Imbriglio, J. E.; Miller, S. J. Chem. Commun. 2005,
195. (h) Read de Alaniz, J.; Rovis, T. J. Am. Chem. Soc. 2005, 127, 6284.
(i) Nakamura, T.; Hara, O.; Tamura, T.; Makino, K.; Hamada, Y. Synlett
2005, 155. (j) Liu, Q.; Rovis, T. J. Am. Chem. Soc. 2006, 128, 2552. (k)
Mattson, A. E.; Zuhl, A. M.; Reynolds, T. E.; Scheidt, K. A. J. Am. Chem.
Soc. 2006, 128, 4932.
(10) An early report on the transformation of trichloroacetaldehyde to
dichloroacetic acid in the presence of cyanide: Wallach, O. Ann. Chem.
1873, 6, 114.
10.1021/ol0713537 CCC: $37.00
© 2007 American Chemical Society
Published on Web 08/09/2007