Organic Letters
Letter
(i) Arockiam, P. B.; Bruneau, C.; Dixneuf, P. H. Chem. Rev. 2012, 112,
5879−5918. (j) Rouquet, G.; Chatani, N. Angew. Chem., Int. Ed. 2013,
52, 11726−11743. (k) Kakiuchi, F.; Kochi, T.; Murai, S. Synlett 2014,
25, 2390−2414. (l) Zhang, X.-S.; Chen, K.; Shi, Z.-J. Chem. Sci. 2014,
5, 2146−2159. (m) Zhang, M.; Zhang, Y.; Jie, X.; Zhao, H.; Li, G.; Su,
W. Org. Chem. Front. 2014, 1, 843−895.
suggests an isolated allyl cation in the intermediate E, which
can be best interpreted as independent π-allyl platinum and π-
allyl cation systems. Finally, the directing pyridyl group can be
easily removed by using a literature procedure.6c,19 As a
demonstration, 4aa reacted with methyl trifluoromethanesulfo-
nate to give the corresponding methylated pyridinium, which
was subsequently treated with a solution prepared from sodium
and methanol to give 6 in 86% yield (Scheme 8).
(3) For a previous report of platinum-catalyzed ortho-silylation of
aromatic aldimines and related reactions, see: (a) Williams, N. A.;
Uchimaru, Y.; Tanaka, M. J. Chem. Soc., Chem. Commun. 1995, 1129−
1130. (b) Tsukada, N.; Hartwig, J. F. J. Am. Chem. Soc. 2005, 127,
5022−5023.
Scheme 8. Removal of Directing Pyridyl Group
(4) For Pt-catalyzed sp3 C−H functionalizations, see: (a) Periana, R.
A.; Taube, D. J.; Gamble, S.; Taube, H.; Satoh, T.; Fujii, H. Science
1998, 280, 560−564. (b) Yang, S.; Li, Z.; Jian, X.; He, C. Angew.
Chem., Int. Ed. 2009, 48, 3999−4001.
(5) Wu, X.-F. Chem. - Eur. J. 2015, 21, 12252−12265.
(6) (a) Fang, P.; Li, M.; Ge, H. J. Am. Chem. Soc. 2010, 132, 11898−
11899. (b) Yang, Z.; Chen, X.; Liu, J.; Gui, Q.; Xie, K.; Li, M.; Tan, Z.
Chem. Commun. 2013, 49, 1560−1562. (c) Yao, J.; Feng, R.; Wu, Z.;
Liu, Z.; Zhang, Y. Adv. Synth. Catal. 2013, 355, 1517−1522. (d) Miao,
J.; Ge, H. Org. Lett. 2013, 15, 2930−2933.
(7) (a) Jia, X.; Zhang, S.; Wang, W.; Luo, F.; Cheng, J. Org. Lett.
2009, 11, 3120−3123. (b) Basle, O.; Bidange, J.; Shuai, Q.; Li, C.-J.
Adv. Synth. Catal. 2010, 352, 1145−1149. (c) Wu, Y.; Li, B.; Mao, F.;
Li, X.; Kwong, F. Y. Org. Lett. 2011, 13, 3258−3261. (d) Tian, Q.; He,
P.; Kuang, C. Org. Biomol. Chem. 2014, 12, 7474−7477. (e) Chu, J.-H.;
Chen, S.-T.; Chiang, M.-F.; Wu, M.-J. Organometallics 2015, 34, 953−
966.
(8) (a) Xiao, F.; Shuai, Q.; Zhao, F.; Basle, O.; Deng, G.; Li, C. J. Org.
́
Lett. 2011, 13, 1614−1617. (b) Yuan, Y.; Chen, D.; Wang, X. Adv.
Synth. Catal. 2011, 353, 3373−3379.
(9) Han, S.; Sharma, S.; Park, J.; Kim, M.; Shin, Y.; Mishra, N. K.;
Bae, J. J.; Kwak, J. H.; Jung, Y. H.; Kim, I. S. J. Org. Chem. 2014, 79,
275−284.
(10) Zhang, Q.; Yang, F.; Wu, Y. Chem. Commun. 2013, 49, 6837−
6839.
(11) (a) Zhang, G.; Sun, S.; Yang, F.; Zhang, Q.; Kang, J.; Wu, Y.;
Wu, Y. Adv. Synth. Catal. 2015, 357, 443−450. (b) Behera, A.; Ali, W.;
Guin, S.; Khatun, N.; Mohanta, P. R.; Patel, B. K. RSC Adv. 2015, 5,
33334−33338.
(12) (a) Khemnar, A. B.; Bhanage, B. M. Eur. J. Org. Chem. 2014,
2014, 6746−6752. (b) Khatun, N.; Banerjee, A.; Santra, S. K.; Behera,
A.; Patel, B. K. RSC Adv. 2014, 4, 54532−54538.
(13) Yin, Z.; Sun, P. J. Org. Chem. 2012, 77, 11339−11344.
(14) (a) Kochi, T.; Urano, S.; Seki, H.; Mizushima, E.; Sato, M.;
Kakiuchi, F. J. Am. Chem. Soc. 2009, 131, 2792−2793. (b) Kochi, T.;
Tazawa, A.; Honda, K.; Kakiuchi, F. Chem. Lett. 2011, 40, 1018−1020.
(c) Liu, P. M.; Frost, C. G. Org. Lett. 2013, 15, 5862−5865.
(15) Mamone, P.; Danoun, G.; Gooßen, L. J. Angew. Chem., Int. Ed.
2013, 52, 6704−6708.
(16) Lu, J.; Zhang, H.; Chen, X.; Liu, H.; Jiang, Y.; Fu, H. Adv. Synth.
Catal. 2013, 355, 529−536.
(17) (a) Carroll, J.; Woolard, H. G.; Mroz, R.; Nason, C. A.; Huo, S.
Organometallics 2016, 35, 1313−1322. (b) Carroll, J.; Gagnier, J. P.;
Garner, A. W.; Moots, J. G.; Pike, R. D.; Li, Y.; Huo, S. Organometallics
2013, 32, 4828−4836.
(18) Albrecht, M.; Spek, A. L.; van Koten, G. J. Am. Chem. Soc. 2001,
123, 7233−7246.
(19) Chu, J.-H.; Lin, P.-S.; Wu, M.-J. Organometallics 2010, 29,
4058−40.
In summary, we have discovered a unique, platinum-
catalyzed, ortho C−H acylation reaction. The reaction requires
neither an oxidant nor other additives. Although the reactions
were carried out in air, the exclusion of oxygen did not affect
the reaction (Table S1). The facile double acylation is quite
remarkable. Further experimental and theoretical studies are
necessary to understand the scope and mechanism of this
platinum-catalyzed C−H acylation reaction.
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
Experimental details, characterization of new com-
pounds, and 1H and 13C NMR spectra of new
AUTHOR INFORMATION
■
Corresponding Author
ORCID
Notes
The authors declare no competing financial interest.
†L.H. is a visiting student from J. H. Rose High School, 600
West Arlington Boulevard, Greenville, NC 27834.
ACKNOWLEDGMENTS
■
We thank Dr. Kimberly Kew (Department of Chemistry, East
Carolina University) for her assistance in Mass spectrometry.
D.C.M. is grateful for a Burroughs-Wellcome Fellowship.
REFERENCES
■
(1) For ground-breaking work, see: Murai, S.; Kakiuchi, F.; Sekine, S.;
Tanaka, Y.; Kamatani, A.; Sonoda, M.; Chatani, N. Nature 1993, 366,
529−531.
(2) For selected reviews, see: (a) Dyker, G. Angew. Chem., Int. Ed.
1999, 38, 1698−1712. (b) Chen, X.; Engle, K. M.; Wang, D.-H.; Yu, J.-
Q. Angew. Chem., Int. Ed. 2009, 48, 5094−5115. (c) Daugulis, O.; Do,
H.-Q.; Shabashov, D. Acc. Chem. Res. 2009, 42, 1074−1086. (d) Lyons,
T. W.; Sanford, M. S. Chem. Rev. 2010, 110, 1147−1169. (e) Colby, D.
A.; Bergman, R. G.; Ellman, J. A. Chem. Rev. 2010, 110, 624−655.
(f) Sun, C.-L.; Li, B.-J.; Shi, Z.-J. Chem. Rev. 2011, 111, 1293−1314.
(g) Ackermann, L. Chem. Rev. 2011, 111, 1315−1345. (h) Engle, K.
M.; Mei, T.-S.; Wasa, M.; Yu, J.-Q. Acc. Chem. Res. 2012, 45, 788−802.
D
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