Organic Letters
Letter
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Figure 1. Proposed mechanistic pathway.
methylpyridine. The ethoxy radical undergoes a hydrogen
abstraction from diphenylphosphine oxide to afford phosphinoyl
radical. Subsequently, the phosphinoyl radical reacts with the
quinolinone or coumarin substrates to give radical IV, which
undergoes a second SET event with strongly oxidizing
quinolinone substrate or product radical cations III (+1.71 and
+1.88 V vs SCE, respectively) to regenerate ground-state
substrate or product I. The desired product is produced after
deprotonation of V with base.
In summary, we developed a regioselective phosphonation of
quinolinone and coumarin derivatives using a household CFL
bulb without the need for an external photocatalyst. The reaction
is initiated by the photochemical activity of substrates, and the
resulting products greatly increased the rate through light-
mediated autocatalysis. The current method is compatible with a
broad range of substituents and allows the rapid generation of 3-
phosphonylated derivatives, which are privileged structures in
many biologically active compounds.
ASSOCIATED CONTENT
* Supporting Information
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S
The Supporting Information is available free of charge on the
Experimental procedure and characterization of new
compounds (1H and 13C NMR spectra) (PDF)
AUTHOR INFORMATION
(8) For recent review on EDA complexes, see: Lima, C. G. S.; Lima, T.
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D.; Duarte, M.; Jurberg, I. D.; Paixao, M. W. ACS Catal. 2016, 6, 1389.
Corresponding Author
ORCID
̃
́
́
(9) (a) Arceo, E.; Jurberg, I. D.; Alvarez-Fernandez, A.; Melchiorre, P.
Nat. Chem. 2013, 5, 750. (b) Nappi, M.; Bergonzini, G.; Melchiorre, P.
Angew. Chem., Int. Ed. 2014, 53, 4921. (c) da Silva, G. P.; Ali, A.; da Silva,
R. C.; Jiang, H.; Paixao, M. W. Chem. Commun. 2015, 51, 15110.
̃
Author Contributions
§I.K. and M.M. contributed equally to this work.
Notes
(d) Kandukuri, S. R.; Bahamonde, A.; Chatterjee, I.; Jurberg, I. D.;
Escudero-Adan, E. C.; Melchiorre, P. Angew. Chem., Int. Ed. 2015, 54,
1485.
(10) Silvi, M.; Arceo, E.; Jurberg, I. D.; Cassani, C.; Melchiorre, P. J.
Am. Chem. Soc. 2015, 137, 6120.
(11) Jin, Y.; Yang, H.; Fu, H. Chem. Commun. 2016, 52, 12909.
(12) (a) Pratsch, G.; Lackner, G. L.; Overman, L. E. J. Org. Chem. 2015,
80, 6025. (b) Kim, K.; Min, M.; Hong, S. Adv. Synth. Catal. 2016, 1.
(13) Quint, V.; Morlet-Savary, F.; Lohier, J. F.; Lalevee, J.; Gaumont, A.
C.; Lakhdar, S. J. Am. Chem. Soc. 2016, 138, 7436.
(14) (a) Beatty, J. W.; Douglas, J. J.; Cole, K. P.; Stephenson, C. R. J.
Nat. Commun. 2015, 6, 7919. (b) Beatty, J. W.; Douglas, J. J.; Miller, R.;
McAtee, R. C.; Cole, K. P.; Stephenson, C. R. J. Chem. 2016, 1, 456.
(15) (a) Bockman, T. M.; Lee, K. Y.; Kochi, J. K. J. Chem. Soc., Perkin
Trans. 2 1992, 1581.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
This research was supported financially by the Institute for Basic
Science (IBS-R010-G1).
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