Organic Letters
Letter
(h) Zheng, P.; Lieberman, B. P.; Choi, S. R.; Ploessl, K.; Kung, H. F.
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80% yield. The formation of this species is consistent with a
retro-Claisen pathway.12
Bioorg. Med. Chem. Lett. 2011, 21, 3435. (i) Jones, K. M.; Karier, P.;
Klussmann, M. ChemCatChem 2012, 4, 51. (j) Zhang, G.; Wang, S.;
Ma, Y.; Kong, W.; Wang, R. Adv. Synth. Catal. 2013, 355, 874.
(3) Selected reviews on amine C−H functionalization, including
redox-neutral approaches: (a) Murahashi, S.-I. Angew. Chem., Int. Ed.
Engl. 1995, 34, 2443. (b) Matyus, P.; Elias, O.; Tapolcsanyi, P.;
Polonka-Balint, A.; Halasz-Dajka, B. Synthesis 2006, 2006, 2625.
(c) Campos, K. R. Chem. Soc. Rev. 2007, 36, 1069. (d) Murahashi, S.-
I.; Zhang, D. Chem. Soc. Rev. 2008, 37, 1490. (e) Li, C.-J. Acc. Chem.
Res. 2009, 42, 335. (f) Jazzar, R.; Hitce, J.; Renaudat, A.; Sofack-
Kreutzer, J.; Baudoin, O. Chem. - Eur. J. 2010, 16, 2654. (g) Yeung, C.
S.; Dong, V. M. Chem. Rev. 2011, 111, 1215. (h) Pan, S. C. Beilstein J.
Org. Chem. 2012, 8, 1374. (i) Mitchell, E. A.; Peschiulli, A.; Lefevre,
N.; Meerpoel, L.; Maes, B. U. W. Chem. - Eur. J. 2012, 18, 10092.
(j) Zhang, C.; Tang, C.; Jiao, N. Chem. Soc. Rev. 2012, 41, 3464.
(k) Jones, K. M.; Klussmann, M. Synlett 2012, 2012, 159. (l) Peng, B.;
Maulide, N. Chem. - Eur. J. 2013, 19, 13274. (m) Platonova, A. Y.;
Glukhareva, T. V.; Zimovets, O. A.; Morzherin, Y. Y. Chem. Heterocycl.
Compd. 2013, 49, 357. (n) Prier, C. K.; Rankic, D. A.; MacMillan, D.
W. C. Chem. Rev. 2013, 113, 5322. (o) Girard, S. A.; Knauber, T.; Li,
C.-J. Angew. Chem., Int. Ed. 2014, 53, 74. (p) Haibach, M. C.; Seidel,
D. Angew. Chem., Int. Ed. 2014, 53, 5010. (q) Wang, L.; Xiao, J. Adv.
Synth. Catal. 2014, 356, 1137. (r) Vo, C.-V. T.; Bode, J. W. J. Org.
Chem. 2014, 79, 2809. (s) Seidel, D. Org. Chem. Front. 2014, 1, 426.
(t) Qin, Y.; Lv, J.; Luo, S. Tetrahedron Lett. 2014, 55, 551. (u) Beatty,
J. W.; Stephenson, C. R. J. Acc. Chem. Res. 2015, 48, 1474.
Products of the intramolecular redox-Mannich reaction, in
particularly those shown in Scheme 2, are closely related to a
number of natural products and other bioactive compounds.
For instance, compound 1n is known as tetrabenazine, a drug
used to treat chorea such as Huntington’s disease.13 Enantio-
merically pure (+)-1n is readily available via the resolution
of the racemic mixture by (+)-camphorsulfonic acid.13b
Compound 1i has previously been converted to ( )-proto-
emetinol and ( )-emetin via short synthetic sequences.1a,2c
In conclusion, we have developed an intramolecular redox-
Mannich reaction between cyclic amines and β-ketoaldehydes
as a facile entry to benzo[a]quinolizine-2-one derivatives.
Challenging enolizable β-ketoaldehydes provided the desired
products with useful levels of diastereoselectivity.
ASSOCIATED CONTENT
* Supporting Information
■
(4) Selected reviews on other types of redox-neutral transformations:
(a) Burns, N. Z.; Baran, P. S.; Hoffmann, R. W. Angew. Chem., Int. Ed.
2009, 48, 2854. (b) Mahatthananchai, J.; Bode, J. W. Acc. Chem. Res.
2014, 47, 696. (c) Ketcham, J. M.; Shin, I.; Montgomery, T. P.;
Krische, M. J. Angew. Chem., Int. Ed. 2014, 53, 9142. (d) Huang, H.; Ji,
X.; Wu, W.; Jiang, H. Chem. Soc. Rev. 2015, 44, 1155.
S
The Supporting Information is available free of charge on the
Experimental procedures and characterization data (PDF)
(5) (a) Seidel, D. Acc. Chem. Res. 2015, 48, 317. Selected examples
from our lab: (b) Zhang, C.; De, C. K.; Mal, R.; Seidel, D. J. Am. Chem.
Soc. 2008, 130, 416. (c) Ma, L.; Chen, W.; Seidel, D. J. Am. Chem. Soc.
2012, 134, 15305. (d) Das, D.; Sun, A. X.; Seidel, D. Angew. Chem., Int.
Ed. 2013, 52, 3765. (e) Dieckmann, A.; Richers, M. T.; Platonova, A.
Y.; Zhang, C.; Seidel, D.; Houk, K. N. J. Org. Chem. 2013, 78, 4132.
(f) Chen, W.; Seidel, D. Org. Lett. 2014, 16, 3158. (g) Richers, M. T.;
Breugst, M.; Platonova, A. Y.; Ullrich, A.; Dieckmann, A.; Houk, K. N.;
Seidel, D. J. Am. Chem. Soc. 2014, 136, 6123. (h) Kang, Y.; Richers, M.
T.; Sawicki, C. H.; Seidel, D. Chem. Commun. 2015, 51, 10648. (i) Ma,
L.; Seidel, D. Chem. - Eur. J. 2015, 21, 12908. (j) Kang, Y.; Chen, W.;
Breugst, M.; Seidel, D. J. Org. Chem. 2015, 80, 9628.
AUTHOR INFORMATION
Corresponding Author
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
Financial support from the NIH−NIGMS (R01GM101389) is
gratefully acknowledged.
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(6) Related studies by others, examples: (a) Zheng, Q.-H.; Meng, W.;
Jiang, G.-J.; Yu, Z.-X. Org. Lett. 2013, 15, 5928. (b) Lin, W.; Cao, T.;
Fan, W.; Han, Y.; Kuang, J.; Luo, H.; Miao, B.; Tang, X.; Yu, Q.; Yuan,
W.; Zhang, J.; Zhu, C.; Ma, S. Angew. Chem., Int. Ed. 2014, 53, 277.
(c) Haldar, S.; Mahato, S.; Jana, C. K. Asian J. Org. Chem. 2014, 3, 44.
(d) Rahman, M.; Bagdi, A. K.; Mishra, S.; Hajra, A. Chem. Commun.
2014, 50, 2951. (e) Li, J.; Wang, H.; Sun, J.; Yang, Y.; Liu, L. Org.
Biomol. Chem. 2014, 12, 2523. (f) Lin, W.; Ma, S. Org. Chem. Front.
2014, 1, 338. (g) Mahato, S.; Haque, M. A.; Dwari, S.; Jana, C. K. RSC
Adv. 2014, 4, 46214. (h) Mandal, S.; Mahato, S.; Jana, C. K. Org. Lett.
2015, 17, 3762. (i) Haldar, S.; Roy, S. K.; Maity, B.; Koley, D.; Jana, C.
K. Chem. - Eur. J. 2015, 21, 15290. (j) Shao, G.; He, Y.; Xu, Y.; Chen,
J.; Yu, H.; Cao, R. Eur. J. Org. Chem. 2015, 2015, 4615. (k) Cheng, Y.-
F.; Rong, H.-J.; Yi, C.-B.; Yao, J.-J.; Qu, J. Org. Lett. 2015, 17, 4758.
(7) Other recent examples of mechanistically distinct, redox-neutral
amine C−H functionalization: (a) He, Y.-P.; Wu, H.; Chen, D.-F.; Yu,
J.; Gong, L.-Z. Chem. - Eur. J. 2013, 19, 5232. (b) Kang, Y. K.; Kim, D.
Y. Chem. Commun. 2014, 50, 222. (c) Mori, K.; Kurihara, K.; Akiyama,
T. Chem. Commun. 2014, 50, 3729. (d) Mori, K.; Kurihara, K.; Yabe,
S.; Yamanaka, M.; Akiyama, T. J. Am. Chem. Soc. 2014, 136, 3744.
(e) Cao, W.; Liu, X.; Guo, J.; Lin, L.; Feng, X. Chem. - Eur. J. 2015, 21,
1632. (f) Wang, P.-F.; Jiang, C.-H.; Wen, X.; Xu, Q.-L.; Sun, H. J. Org.
Chem. 2015, 80, 1155.
REFERENCES
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