Organic Letters
Letter
start-up funding from West China Hospital, Sichuan
University.
REFERENCES
■
(1) (a) Robak, M. T.; Herbage, M. A.; Ellman, J. A. Chem. Rev. 2010,
110, 3600. (b) Kobayashi, S.; Mori, Y.; Fossey, J. S.; Salter, M. M.
́
́
Chem. Rev. 2011, 111, 2626. (c) Yus, M.; Gonzalez-Gomez, J. C.;
́
Foubelo, F. Chem. Rev. 2011, 111, 7774. (d) Yus, M.; Gonzalez-
́
Gomez, J. C.; Foubelo, F. Chem. Rev. 2013, 113, 5595. (e) Kumagai,
N.; Shibasaki, M. Bull. Chem. Soc. Jpn. 2015, 88, 503.
Figure 1. Transition state proposal for the intramolecular allylation
reaction.
(2) (a) Cram, D. J.; Guthrie, R. D. J. Am. Chem. Soc. 1966, 88, 5760.
̈
(b) Kauffmann, T.; Koppelmann, E.; Berg, H. Angew. Chem., Int. Ed.
Engl. 1970, 9, 163.
(3) (a) Seebach, D. Angew. Chem., Int. Ed. Engl. 1979, 18, 239.
(b) Romanov-Michailidis, F.; Rovis, T. Nature 2015, 523, 417.
(c) Waser, M.; Novacek, J. Angew. Chem., Int. Ed. 2015, 54, 14228.
(4) Isomerization: (a) Liu, M.; Li, J.; Xiao, X.; Xie, Y.; Shi, Y. Chem.
Commun. 2013, 49, 1404. (b) Wu, Y.; Deng, L. J. Am. Chem. Soc.
2012, 134, 14334. (c) Zhou, X.; Wu, Y.; Deng, L. J. Am. Chem. Soc.
2016, 138, 12297.
(5) (a) Tang, S.; Park, J. Y.; Yeagley, A. A.; Sabat, M.; Chruma, J.
Org. Lett. 2015, 17, 2042. (b) Liu, X.; Gao, A.; Ding, L.; Xu, J.; Zhao,
B. Org. Lett. 2014, 16, 2118. (c) Matsumoto, M.; Harada, M.;
Yamashita, Y.; Kobayashi, S. Chem. Commun. 2014, 50, 13041.
(d) Chen, Y.-J.; Seki, K.; Yamashita, Y.; Kobayashi, S. J. Am. Chem.
Soc. 2010, 132, 3244. (e) Chen, P.; Yue, Z.; Zhang, J.; Lv, X.; Wang,
L.; Zhang, J. Angew. Chem., Int. Ed. 2016, 55, 13316.
trans-product 3b molecular orbital overlap between Cα and
Cα′ and between Cγ and Cγ′ could be simultaneously
achieved. Such favorable interaction between Cγ and Cγ′
might lower the overall free energy of 2b. On the other hand,
in the TS that gives the cis-product, this secondary orbital
overlap is inaccessible.
In summary, we have developed an umpolung allylation
strategy to prepare 3-vinyl-4-aminochromanes and 3-vinyl-4-
aminotetrahydroquinolines. This transformation exhibits high
trans-selectivity, which is complementary to the existing cis-
selective intramolecular cyclization processes. Importantly, our
transformation could be effected by palladium catalysis or
under transition-metal-free conditions. A model rationalizing
the observed stereoselectivity is proposed. Further inves-
tigations regarding the scope and enantioselective variants of
the current protocol are underway.
(6) (a) Li, M.; Berritt, S.; Walsh, P. J. Org. Lett. 2014, 16, 4312.
(b) Li, M.; Yucel, B.; Adrio, J.; Bellomo, A.; Walsh, P. J. Chem. Sci.
́
2014, 5, 2383. (c) Li, M.; Gonzalez-Esguevillas, M.; Berritt, S.; Yang,
X.; Bellomo, A.; Walsh, P. J. Angew. Chem., Int. Ed. 2016, 55, 2825.
(d) Niwa, T.; Suehiro, T.; Yorimitsu, H.; Oshima, K. Tetrahedron
2009, 65, 5125. (e) Fernandez-Salas, J. A.; Marelli, E.; Nolan, S. P.
Chem. Sci. 2015, 6, 4973. (f) Niwa, T.; Yorimitsu, H.; Oshima, K. Org.
ASSOCIATED CONTENT
* Supporting Information
■
S
́
Lett. 2008, 10, 4689. (g) Li, M.; Yucel, B.; Jimenez, J.; Rotella, M.; Fu,
Y.; Walsh, P. J. Adv. Synth. Catal. 2016, 358, 1910. (h) Zhu, Y.;
Buchwald, S. L. J. Am. Chem. Soc. 2014, 136, 4500. (i) Li, M.; Berritt,
S.; Matuszewski, L.; Deng, G.; Pascual-Escudero, A.; Panetti, G. B.;
Poznik, M.; Yang, X.; Chruma, J. J.; Walsh, P. J. J. Am. Chem. Soc.
2017, 139, 16327. (j) Li, M.; Gutierrez, O.; Berritt, S.; Pascual-
The Supporting Information is available free of charge on the
Detailed experimental procedures, characterization data,
Escudero, A.; Yesi̧ lci̧ men, A.; Yang, X.; Adrio, J.; Huang, G.;
Nakamaru-Ogiso, E.; Kozlowski, M. C.; Walsh, P. J. Nat. Chem.
2017, 9, 997. (k) Shao, X.; Li, K.; Malcolmson, S. J. J. Am. Chem. Soc.
2018, 140, 7083. (l) Li, K. N.; Shao, X. X.; Tseng, L.; Malcolmson, S.
J. J. Am. Chem. Soc. 2018, 140, 598. (m) Daniel, P. E.; Weber, A. E.;
Malcolmson, S. J. Org. Lett. 2017, 19, 3490. (n) Li, K. N.; Weber, A.
E.; Tseng, L.; Malcolmson, S. J. Org. Lett. 2017, 19, 4239.
Accession Codes
CCDC 1547232 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
(7) Fields, W. H.; Chruma, J. J. Org. Lett. 2010, 12, 316.
(8) Allylation: (a) Burger, E. C.; Tunge, J. A. J. Am. Chem. Soc. 2006,
128, 10002. (b) Yeagley, A. A.; Chruma, J. J. Org. Lett. 2007, 9, 2879.
(c) Li, Z.; Jiang, Y.-Y.; Yeagley, A. A.; Bour, J. P.; Liu, L.; Chruma, J.
J.; Fu, Y. Chem. - Eur. J. 2012, 18, 14527. (d) Qian, X.; Ji, P.; He, C.;
Zirimwabagabo, J.-O.; Archibald, M. M.; Yeagley, A. A.; Chruma, J. J.
Org. Lett. 2014, 16, 5228. (e) Liu, J.; Cao, C.-G.; Sun, H.-B.; Zhang,
X.; Niu, D. J. Am. Chem. Soc. 2016, 138, 13103. (f) Su, Y.-L.; Li, Y.-H.;
Chen, Y.-G.; Han, Z.-Y. Chem. Commun. 2017, 53, 1985. (g) Zhuo,
AUTHOR INFORMATION
■
Corresponding Author
ORCID
Author Contributions
‡M.Z. and X.P. contributed equally.
Notes
C.-X.; Furstner, A. J. J. Am. Chem. Soc. 2018, 140, 10514. (h) Wan, L.
̈
Q.; Tian, L.; Liu, J.; Niu, D. W. Synlett 2017, 28, 2051.
(9) Michael addition: (a) Wu, Y.; Hu, L.; Li, Z.; Deng, L. Nature
2015, 523, 445. (b) Hu, L.; Wu, Y.; Li, Z.; Deng, L. J. Am. Chem. Soc.
2016, 138, 15817. (c) Hu, B.; Deng, L. Angew. Chem., Int. Ed. 2018,
57, 2233. (d) Li, Z.; Hu, B.; Wu, Y. W.; Fei, C.; Deng, L. Proc. Natl.
Acad. Sci. U. S. A. 2018, 115, 1730.
The authors declare no competing financial interest.
(10) (a) Kang, H.-Y.; Yu, Y.-K. Bull. Korean Chem. Soc. 2004, 25,
1627. (b) Samanta, D.; Kargbo, R. B.; Cook, G. R. J. Org. Chem. 2009,
74, 7183. (c) Su, L.; Zhu, T.-S.; Xu, M.-H. Org. Lett. 2014, 16, 4118.
(d) Nguyen, V. C.; Kim, Y.-T.; Yu, Y.-K.; Kang, H.-Y. Bull. Korean
Chem. Soc. 2005, 26, 711. (e) Kumar, D.; Vemula, S. R.;
ACKNOWLEDGMENTS
■
Financial support for this project was provided by the 1000-
Youth Talents Program, the National Natural Science
Foundation of China (Nos. 21602145 and 21772125), and
C
Org. Lett. XXXX, XXX, XXX−XXX