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Letter
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concomitant release of 4-FC6H4I. The formation of this cation
intermediate was further supported by the fact that the
replacement of the Me in 1a with CF3 completely suppressed
the reaction (Scheme S2D). Finally, under the assistance of a
suitable base, the E1 elimination from this intermediate gives
thermodynamically stable product 2a. Further validation of this
proposed mechanism is still ongoing in our laboratory.
In conclusion, we describe here the first hypervalent
iodine(III)-mediated intramolecular decarboxylative Heck-
type reaction of 2-vinyl-phenyl oxamic acids. Various 2-
quinolinones were synthesized in moderate to excellent yields
at room temperature using this method. This protocol is metal-
free and operationally simple, displays excellent chemo-
selectivity and functional group compatibility, and features a
distinct ring-strain-enabled radical decarboxylation mechanism.
These advantages will likely render this reaction a useful tool for
the synthesis of medicinally valuable 2-quinolinone structures
and the design of new decarboxylative coupling reactions.
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ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
Experimental details and characterization data (PDF)
AUTHOR INFORMATION
Corresponding Authors
■
(8) (a) Xia, H.-D.; Zhang, Y.-D.; Wang, Y.-H.; Zhang, C. Org. Lett.
́
2018, 20, 4052−4056. (b) Fra, L.; Millan, A.; Souto, J. A.; Mun
̃
iz, K.
ORCID
Angew. Chem., Int. Ed. 2014, 53, 7349−7353.
(9) (a) Zhang, X.; MacMillan, D. W. C. J. Am. Chem. Soc. 2016, 138,
13862−13865. (b) Huang, H.; Yu, C.; Zhang, Y.; Zhang, Y.; Mariano,
P. S.; Wang, W. J. Am. Chem. Soc. 2017, 139, 9799−9802.
(10) Morimoto, K.; Ohnishi, Y.; Koseki, D.; Nakamura, A.; Dohi, T.;
Kita, Y. Org. Biomol. Chem. 2016, 14, 8947−8951.
Notes
(11) Zhdankin, V. V.; Koposov, A. E.; Smart, J. T.; Tykwinski, R. R.;
McDonald, R.; Morales-Izquierdo, A. J. Am. Chem. Soc. 2001, 123,
4095−4096.
The authors declare no competing financial interest.
(12) (a) Kiprof, P. ARKIVOC 2005, 4, 19−25. (b) Zhdankin, V. V.;
Krasutsky, A. P.; Kuehl, C. J.; Simonsen, A. J.; Woodward, J. K.;
Mismash, B.; Bolz, J. T. J. Am. Chem. Soc. 1996, 118, 5192−5197.
(13) (a) Minisci, F.; Vismara, E.; Fontana, F.; Barbosa, M. C. N.
Tetrahedron Lett. 1989, 30, 4569−4572. (b) Genovino, J.; Lian, Y.;
ACKNOWLEDGMENTS
■
Financial support from the program of the National Natural
Science Foundation of China (21602060, 21871086, Y.-Q.Z.;
21572055, 21738002, W.W.) and the Chinese Fundamental
Research Funds for the Central Universities (ECUST:
WY1714033) is gratefully acknowledged.
́
Zhang, Y.; Hope, T. O.; Juneau, A.; Gagne, Y.; Ingle, G.; Frenette, M.
Org. Lett. 2018, 20, 3229−3232. (c) Togo, H.; Aoki, M.; Yokoyama, M.
Tetrahedron Lett. 1991, 32, 6559−6562.
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