Organic Letters
Letter
P.; Mugrage, B.; DeLuca, M. R.; Cain, G. A. J. Am. Chem. Soc. 1990,
112, 5220. (d) Kitajima, M.; Watanabe, K.; Maeda, H.; Kogure, N.;
Takayama, H. Org. Lett. 2016, 18, 1912.
(5) Kump, W. G.; Patel, M. B.; Rowson, J. M.; Schmid, H. Helv.
Chim. Acta 1964, 47, 1497.
allene C delivers the π-allylpalladium species D, which reacts
with substituted indole 1a to give the dearomative product 3aa
together with Pd(0) (cycle II).
In summary, we have developed a palladium-catalyzed
dearomative allylic alkylation of indoles with alkynes to
construct indolenines with C3-quarternary centers. The in
situ formed arylallene intermediate omitted the need of
installing leaving groups to the allylic compounds and
employing extra oxidants to oxidize the allylic C−H bonds.
The reaction exhibited good functional group tolerance as well
as high atom economy. Moreover, our protocol was expanded
to synthesize pyrroloindoline and furanoindoline frameworks.
Further studies on the asymmetric synthesis are currently
underway in our laboratory.
(6) For selected reviews, see: (a) Lop
́
ez Ortiz, F.; Iglesias, M. J.;
Fernandez, I.; Andujar Sanchez, C. M.; Ruiz Gom
́
́
́
ez, G. Chem. Rev.
́
2007, 107, 1580. (b) Zhuo, C.-X.; Zheng, C.; You, S.-L. Acc. Chem. Res.
2014, 47, 2558. (c) Asymmetric Dearomatization Reactions, 1st ed.;
You, S.-L., Eds.; Wiley−VCH: Weinheim, 2016.
(7) For selected examples, see: (a) Kimura, M.; Futamata, M.; Mukai,
R.; Tamaru, Y. J. Am. Chem. Soc. 2005, 127, 4592. (b) Trost, B. M.;
Quancard, J. J. Am. Chem. Soc. 2006, 128, 6314. (c) Kagawa, N.;
Malerich, J. P.; Rawal, V. H. Org. Lett. 2008, 10, 2381. (d) Wu, Q.-F.;
He, H.; Liu, W.-B.; You, S.-L. J. Am. Chem. Soc. 2010, 132, 11418.
(e) Wu, Q.-F.; Zheng, C.; You, S.-L. Angew. Chem., Int. Ed. 2012, 51,
1680. (f) Cao, T.; Linton, E. C.; Deitch, J.; Berritt, S.; Kozlowski, M.
C. J. Org. Chem. 2012, 77, 11034. (g) Chen, J.; Cook, M. J. Org. Lett.
2013, 15, 1088. (h) Kaiser, T. M.; Yang, J. Eur. J. Org. Chem. 2013,
2013, 3983. (i) Liu, Y.; Du, H. Org. Lett. 2013, 15, 740.
(j) Montgomery, T. D.; Zhu, Y.; Kagawa, N.; Rawal, V. H. Org. Lett.
2013, 15, 1140. (k) Gao, R.-D.; Liu, C.; Dai, L.-X.; Zhang, W.; You, S.-
L. Org. Lett. 2014, 16, 3919.
(8) (a) Jia, M.; Cera, G.; Perrotta, D.; Monari, M.; Bandini, M. Chem.
- Eur. J. 2014, 20, 9875. (b) Romano, C.; Jia, M.; Monari, M.; Manoni,
E.; Bandini, M. Angew. Chem., Int. Ed. 2014, 53, 13854. (c) Rocchigiani,
L.; Jia, M.; Bandini, M.; Macchioni, A. ACS Catal. 2015, 5, 3911.
(d) Manoni, E.; De Nisi, A.; Bandini, M. Pure Appl. Chem. 2016, 88,
207.
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
1H and 13C NMR spectra for all new compounds (PDF)
AUTHOR INFORMATION
Corresponding Authors
■
Author Contributions
†S.G. and Z.W. contributed equally.
(9) Zhang, H.; Hu, R.-B.; Liu, N.; Li, S.-X.; Yang, S.-D. Org. Lett.
2016, 18, 28.
(10) For selected reviews, see: (a) Trost, B. M.; Van Vranken, D. L.
Chem. Rev. 1996, 96, 395. (b) Trost, B. M. Chem. Pharm. Bull. 2002,
50, 1. (c) Trost, B. M.; Crawley, M. L. Chem. Rev. 2003, 103, 2921.
(d) Engelin, C. J.; Fristrup, P. Molecules 2011, 16, 951. (e) Le Bras, J.;
Muzart, J. Eur. J. Org. Chem. 2016, 2016, 2565. (f) Butt, N. A.; Zhang,
W. Chem. Soc. Rev. 2015, 44, 7929.
Notes
The authors declare no competing financial interest.
(11) For review, see: (a) Yamamoto, Y.; Radhakrishnan, U. Chem.
Soc. Rev. 1999, 28, 199. For selected examples, see: (b) Kadota, I.;
Shibuya, A.; Gyoung, Y. S.; Yamamoto, Y. J. Am. Chem. Soc. 1998, 120,
10262. (c) Lutete, L. M.; Kadota, I.; Yamamoto, Y. J. Am. Chem. Soc.
2004, 126, 1622. (d) Chen, Q.-A.; Cruz, F. A.; Dong, V. M. J. Am.
Chem. Soc. 2015, 137, 3157. (e) Chen, Q.-A.; Chen, Z.; Dong, V. M. J.
Am. Chem. Soc. 2015, 137, 8392. (f) Cruz, F. A.; Chen, Z.; Kurtoic, S.
I.; Dong, V. M. Chem. Commun. 2016, 52, 5836. (g) Gellrich, U.;
ACKNOWLEDGMENTS
■
Generous financial support from the National Natural Science
Foundation of China (NSFC21572272 and NSFC21502232),
the Natural Science Foundation of Jiangsu Province
(BK20140655), the Foundation of State Key Laboratory of
Natural Medicines (ZZYQ201605), and the Innovative
Research Team in University (IRT_15R63) is gratefully
acknowledged.
Meißner, A.; Steffani, A.; Kahny, M.; Drexler, H.-J.; Heller, D.;
̈
Plattner, D. A.; Breit, B. J. Am. Chem. Soc. 2014, 136, 1097. (h) Xu, K.;
Khakyzadeh, V.; Bury, T.; Breit, B. J. Am. Chem. Soc. 2014, 136, 16124.
REFERENCES
■
(i) Koschker, P.; Kahny, M.; Breit, B. J. Am. Chem. Soc. 2015, 137,
̈
(1) For selected reviews, see: (a) Roche, S. P.; Porco, J. A., Jr. Angew.
Chem., Int. Ed. 2011, 50, 4068. (b) James, M. J.; O’Brien, P.; Taylor, R.
J. K.; Unsworth, W. P. Chem. - Eur. J. 2016, 22, 2856. For selected
examples, see: (c) Kam, T.-S.; Choo, Y.-M. J. Nat. Prod. 2004, 67, 547.
(d) Nakazaki, A.; Hara, Y.; Kajii, S. Heterocycles 2013, 87, 611.
(e) Yang, X.-W.; Luo, X.-D.; Lunga, P. K.; Zhao, Y.-L.; Qin, X.-J.;
Chen, Y.-Y.; Liu, L.; Li, X.-N.; Liu, Y.-P. Tetrahedron 2015, 71, 3694.
(2) (a) Schnoes, H. K.; Biemann, K.; Mokry, J.; Kompis, I.;
Chatterjee, A.; Ganguli, G. J. Org. Chem. 1966, 31, 1641. (b) Komatsu,
Y.; Yoshida, K.; Ueda, H.; Tokuyama, H. Tetrahedron Lett. 2013, 54,
377. (c) Moreno, J.; Picazo, E.; Morrill, L. A.; Smith, J. M.; Garg, N. K.
J. Am. Chem. Soc. 2016, 138, 1162. (d) Nishiyama, D.; Ohara, A.;
Chiba, H.; Kumagai, H.; Oishi, S.; Fujii, N.; Ohno, H. Org. Lett. 2016,
18, 1670.
(3) (a) Anthoni, U.; Chevolot, L.; Larsen, C.; Nielsen, P. H.;
Christophersen, C. J. Org. Chem. 1987, 52, 4709. (b) Baran, P. S.;
Shenvi, R. A.; Mitsos, C. A. Angew. Chem., Int. Ed. 2005, 44, 3714.
(c) Baran, P. S.; Shenvi, R. A. J. Am. Chem. Soc. 2006, 128, 14028.
(4) For selected examples, see: (a) Liu, C.-T.; Wang, Q.-W.; Wang,
C.-H. J. Am. Chem. Soc. 1981, 103, 4634. (b) Khuong-Huu, F.;
Chiaroni, A.; Riche, C. Tetrahedron Lett. 1981, 22, 733. (c) Magnus,
3131. (j) Beck, T. M.; Breit, B. Org. Lett. 2016, 18, 124. (k) Li, C.;
Grugel, C. P.; Breit, B. Chem. Commun. 2016, 52, 5840. (l) Haydl, A.
M.; Hilpert, L. J.; Breit, B. Chem. - Eur. J. 2016, 22, 6547.
(12) (a) Zhao, L.; Li, Z.; Chang, L.; Xu, J.; Yao, H.; Wu, X. Org. Lett.
2012, 14, 2066. (b) Gao, S.; Yang, C.; Huang, Y.; Zhao, L.; Wu, X.;
Yao, H.; Lin, A. Org. Biomol. Chem. 2016, 14, 840.
(13) For selected examples, see: (a) Crich, D.; Banerjee, A. Acc.
Chem. Res. 2007, 40, 151. (b) Suzuki, T.; Choi, J.-H.; Kawaguchi, T.;
Yamashita, K.; Morita, A.; Hirai, H.; Nagai, K.; Hirose, T.; Omura, S.;
̅
Sunazuka, T.; Kawagishi, H. Bioorg. Med. Chem. Lett. 2012, 22, 4246.
(c) Subramaniam, G.; Hiraku, O.; Hayashi, M.; Koyano, T.;
Komiyama, K.; Kam, T.-S. J. Nat. Prod. 2007, 70, 1783. (d) Bunders,
C.; Cavanagh, J.; Melander, C. Org. Biomol. Chem. 2011, 9, 5476.
(14) Lin, A.; Yang, J.; Hashim, M. Org. Lett. 2013, 15, 1950.
(15) (a) Trost, B. M.; Rise, F. J. Am. Chem. Soc. 1987, 109, 3161.
(b) Trost, B. M.; Schmidt, T. J. Am. Chem. Soc. 1988, 110, 2301.
(c) Trost, B. M.; Brieden, W.; Baringhaus, K. H. Angew. Chem., Int. Ed.
Engl. 1992, 31, 1335. (d) Patil, N. T.; Song, D.; Yamamoto, Y. Eur. J.
Org. Chem. 2006, 2006, 4211.
D
Org. Lett. XXXX, XXX, XXX−XXX