Journal of the American Chemical Society
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A.; Lin, C.ꢀC.; Hwu, J. R.; Hwang, K. C. Green Chem. 2015,
undergoes radical cleavage to extrude the CO2 and generates the
hydroxyl substituted quinone methide 13. Ketoꢀenol tautomerism
(via aromatization) then leads to the formation of aryl ketone (3a).
By using a ferrioxalate actinometer as a reference for compariꢀ
son,23 the quantum yield for the formation of aryketone 3a was
determined to be 0.7525, suggesting that no chain process was
involved in the current photoredox reactions (see S.I. for details
for quantum yield measurements).
17, 1113: (c) Sagadevan, A.; Hwang, K. C. Adv. Synth. Catal.
2012, 354, 3421: (d) Ragupathi, A.; Sagadevan, A.; Lin, C.ꢀC.;
Hwu, J. R.; Hwang, K. C. Chem. Commun. 2016, 52, 11756: (e)
Sagadevan,A.; Lyu, P. C.; Hwang, K. C., Green Chem, 2016,
18, 4526: (f) Sagadevan, A.; Charpe, V. P.; Hwang, K. C.
Catal. Sci. Technol. 2016, 6, 7688: (g) Ragupathi, A.; Charpe,
V. P.; Sagadevan, A.; Hwang, K. C. Adv. Synth. Catal. 2016,
DOI 10.1002/adsc.201600925.
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(5) (a) Walter, M. W. Nat. Prod. Rep. 2002, 19, 278: (b) Bioorganꢀ
ic Chemistry, 3rd edn., (Ed.: H. Dugas), Springer Verlag, New
York, 1996: (c) Kamat, P. V. Chem. Rev. 1993, 93, 267.
(6) Singh, J.; Satyamurthi, N.; Aidhen, I. S. J. Prakt. Chem. 2000,
342, 340.
Scheme 3. Proposed reaction mechanism
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(7) Ruan. J.; Saidi. O.; Lggo. J. A.; Xiao. J. A. J. Am. Chem. Soc.
2008, 130, 10510.
(8) Lindh, J.; Sjöberg, P. J. R.; Larhed, M. Angew. Chem., Int. Ed.
2010, 49, 7733.
(9) Gooßen, L. J.; Rudolphi, F.; Oppel, C.; Rodríguez, N. Angew.
Chem., Int. Ed. 2008, 47, 3043.
(10) Chu, L.; Lipshultz, J. M.; MacMillan, D. W. C. Angew. Chem.,
Int. Ed. 2015, 54, 7929.
(11) Chen, F.; Wang, T.; Jiao, N. Chem. Rev. 2014, 114, 8613.
(12) (a) Chen, Z.; Zeng, H.; Girard, S. A.; Wang, F.; Chen, N.; Li,
C.ꢀJ. Angew. Chem., Int. Ed. 2015, 54, 14487: (b) Zakzeski, J.;
Bruijnincx, P. C. A.; Jongerius, A. L.; Weckhuysen, B. M.
Chem. Rev. 2010, 110, 3552.
(13) Sambiagio, C.; Marsden, S. P.; Blacker, A. J.; McGowan, P. C.
Chem. Soc. Rev. 2014, 43, 3525.
(14) (a) Wyss, D. F.; Arasappan, A.; Senior, M. M.; Wang, Y.ꢀS.;
Beyer, B. M.; Njoroge, F. G.; McCoy, M. A. J. Med. Chem.
2004, 47, 2486: (b) Top, S.; Kaloun, E. B.; Vessières, A.;
Leclercq, G.; Laïos, I.; Ourevitch, M.; Deuschel, C.;
McGlinchey, M. J.; Jaouen, G. ChemBioChem 2003, 4, 754:
(15) (a) Harjani, J. R.; Nara, S. J.; Salunkhe, M. M. Tetrahedron
Lett. 2001, 42, 1979: (b) Jeon, I.; Mangion, I. K. Synlett 2012,
23, 1927.
In summary, we have demonstrated a novel new chemistry to
regioselectively synthesizes hydroxyl functionalized aryl ketones
via visible lightꢀinduced CuClꢀcatalyzed oxidative coupling of
phenol and terminal alkynes at room temperature. The coupling
reaction occurs via the SET process with O2 and C≡C triple cleavꢀ
age, followed by PaternoꢀBuchi type [2+2] cycloaddition reaction.
Overall, 47 examples were demonstrated. This new chemistry is
easily operated using simple and readily available starting materiꢀ
als under mild conditions, and is also applicable for rapid and
efficient preparation of pharmaceutical drugs, such as, pitofenone
and fenofibrate (2 steps with overall yields of 72–76%, which
are far better than other processes reported in the literature (4
steps, 37 and 71% total yields for pitofenone and fenofibrate,
respectively).
(16) Allen, S. E.; Walvoord, R. R.; PadillaꢀSalinas, R.; Kozlowski,
M. C. Chem. Rev. 2013, 113, 6234.
(17) Chinchilla, R.; Najera, C. Chem. Soc. Rev. 2011, 40, 5084.
(18) Lindhardt, A. T.; Simmonsen, R.; Taaning, R. H.; Gøgsig, T.
M.; Nilsson, G. N.; Stenhagen, G.; Elmore, C. S.; Skrydstrup,
T. J. Labelled Compd. Radiopharm. 2012, 55, 411.
(19) (a) BalꢀTembe, S.; Blumbach, J.; Dohadwana, A.; Punekar, N.
S.; Rajgopalan, R.; Rupp, R. H.; Bickel, M. U.S. pat., 5821252,
1998: (b) Guazzi, G. U.S. pat., US2004073058(A1), 2004.
(20) Lima, C. G. S.; de M. Lima, T.; Duarte, M.; Jurberg, I. D.;
Paixão, M. W. ACS Catal. 2016, 6, 1389.
(21) Bosch, E.; Hubig, S. M.; Kochi, J. K. J. Am. Chem. Soc. 1998,
120, 386.
(22) Sawaki, Y.; Foote, C. S. J. Org. Chem. 1983, 48, 4934.
(23) (a) Cismesia, M. A.; Yoon, T.P. Chem. Sci., 2015, 6, 5426: (b)
Pitre, S. P.; McTiernan, C. D.; Vine, W.; DiPucchio, R.;
Grenier, M.; Scaiano, J. C. Sci. Rep. 2015, 5, 16397.
ASSOCIATED CONTENT
Supporting Information. Experimental procedures and characꢀ
terization data are available free of charge via the Internet at
AUTHOR INFORMATION
Notes: The authors declare no competing financial interests.
ACKNOWLEDGMENT
This work was supported by the Ministry of Science & Technoloꢀ
gy, Taiwan.
REFERENCES
(1) (a) Prier, C. K.; Rankic, D. A.; MacMillan, D. W. C. Chem.
Rev. 2013, 113, 5322: (b) Shaw, M. H.; Twilton, J.; MacMilꢀ
lan, D. W. C. J. Org. Chem. 2016, 81, 6898.
(2) (a) Paria, S.; Reiser, O. ChemCatChem 2014, 6, 2477: (b) Reiꢀ
ser, O. Acc. Chem. Res. 2016, 49, 1990.
(3) Kainz, Q. M.; Matier, C. D.; Bartoszewicz, A.; Zultanski, S. L.;
Peters, J. C.; Fu, G. C. Science 2016, 351, 681.
(4) (a) Sagadevan, A.; Ragupathi, A.; Hwang, K. C. Angew.
Chem., Int. Ed. 2015, 54, 13896: (b) Sagadevan, A.; Ragupathi,
4
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