Organic Letters
Letter
(3) Guan, B.-T.; Wang, Y.; Li, B.-J.; Yu, D.-G.; Shi, Z.-J. J. Am. Chem.
Soc. 2008, 130, 14468.
(4) Firouzabadi, H.; Iranpoor, N.; Gholinejad, M.; Samadi, A. J. Mol.
formation of cross-coupling product 3cb (Figures S1−2,
Supporting Information).
ESI-MS analysis unveiled two palladium triazine species
during the reaction course (Supporting Information, Figures
S3−10). The adduct of palladium acetate and triazine ester was
detected as cationic fragment I of m/z = 481.263, in which Pd
might coordinate to the triazine ring.30b,31 The cationic Pd
species with m/z = 525.289 was assigned as the oxidative addition
intermediate IV. Therefore, a catalytic cycle is proposed in
Scheme 5. The triazine ester 1c first chelates Pd(OAc)2, and
intermediate I forms via the N−Pd coordination on triazine
ester. After being reduced by phenylacetylene, the palladium
center oxidatively adds to adjacent C−O bond of 1c, and II and
III form sequentially. The reduced product was identified as
Glaser diyne (m/z = 202.1) by GC−MS. Phenylacetylene enters
the inner sphere of IV via coordination to Pd(II). Since the
triazine activator is basic,32 the deprotonation of the coordinated
phenylacetylene is accelerated as the heterocycle leaves the
coordination sphere of IV. Finally, the reductive elimination
releases 1,3-ynone product 3bc, and the catalytic active Pd(0)
species recycles.
In summary, palladium-catalyzed alkynylation reactions using
carboxylic triazine esters as electrophiles have been developed.
The C−O activation of triazine is so efficient that it enables clean
C−C couplings showing a wide range of functional tolerance and
unprecedented selectivity. The corresponding 1,3-ynones were
synthesized in excellent yields upon reaction with aryl and alkyl
terminal alkynes, respectively. The development of this protocol
with other C−O bond activations and detailed mechanistic
studies are underway in our group.
Catal. A: Chem. 2013, 377, 190.
(5) Quasdorf, K. W.; Antoft-Finch, A.; Liu, P.; Silberstein, A. L.;
Komaromi, A.; Blackburn, T.; Ramgren, S. D.; Houk, K. N.; Snieckus,
V.; Garg, N. K. J. Am. Chem. Soc. 2011, 133, 6352.
(6) Quasdorf, K. W.; Riener, M.; Petrova, K. V.; Garg, N. K. J. Am.
Chem. Soc. 2009, 131, 17748.
(7) Zhao, Y.-L.; Li, Y.; Li, Y.; Gao, L.-X.; Han, F.-S. Chem.Eur. J.
2010, 16, 4991.
(8) Shi, C.; Aldrich, C. C. Org. Lett. 2010, 12, 2286.
(9) Firouzabadi, H.; Iranpoor, N.; Gholinejad, M.; Samadi, A. J. Mol.
Catal. A: Chem. 2013, 377, 190.
(10) (a) Gao, H.; Li, Y.; Zhou, Y.-G.; Han, F.-S.; Lin, Y.-J. Adv. Synth.
Catal. 2011, 353, 309. (b) Zhang, N.; Hoffman, D. J.; Gutsche, N.;
Gupta, J.; Percec, V. J. Org. Chem. 2012, 77, 5956.
(11) Xing, C.-H.; Lee, J.-R.; Tang, Z.-Y.; Zheng, J. R.; Hu, Q. S. Adv.
Synth. Catal. 2011, 353, 2051.
(12) Li, X.-J.; Zhang, J.-L.; Geng, Y.; Jin, Z. J. Org. Chem. 2013, 78,
5078.
(13) (a) Prokopcova, H.; Kappe, C. O. Angew. Chem. 2009, 48, 2276.
(b) Bao, Y. S.; Zhaorigetu, B.; Agula, B.; Baiyin, M.; Jia, M. J. Org. Chem.
2014, 79, 803.
(14) Rosen, B. M.; Quasdorf, K. W.; Wilson, D. A.; Zhang, N.;
Resmerita, A.-M.; Garg, N. K.; Percec, V. Chem. Rev. 2011, 111, 1346.
(15) (a) Unsworth, W. P.; Cuthbertson, J. D.; Taylor, R. J. K. Org. Lett.
2013, 15, 3306. (b) Forsyth, C. J.; Xu, J.; Nguyen, S. T.; Samdal, I. A.;
Briggs, L. R.; Rundberget, T.; Sandvik, M.; Miles, C. O. J. Am. Chem. Soc.
2006, 128, 15114.
(16) (a) Xu, B. H.; Kehr, G.; Frohlich, R.; Wibbeling, B.; Schirmer, B.;
Grimme, S.; Erker, G. Angew. Chem. 2011, 50, 7183. (b) Nicolaou, K. C.;
Sarlah, D.; Shaw, D. M. Angew. Chem., Int. Ed. 2007, 46, 4708.
(17) (a) Shen, J.; Cheng, G.; Cui, X. Chem. Commun. 2013, 49, 10641.
(b) Kirkham, J. D.; Edeson, S. J.; Stokes, S.; Harrity, J. P. A. Org. Lett.
2012, 14, 5354.
ASSOCIATED CONTENT
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S
* Supporting Information
(18) Karpov, A. S.; Merkul, E.; Rominger, F.; Muller, T. J. J. Angew.
Chem., Int. Ed. 2005, 44, 6951.
Experimental details and characterization data. The Supporting
(19) (a) Li, H.; Neumann, H.; Beller, M.; Wu, X. F. Angew. Chem., Int.
Ed. 2014, 53, 3183. (b) Neumann, K. T.; Laursen, S. R.; Lindhardt, A. T.;
Bang-Andersen, B.; Skrydstrup, T. Org. Lett. 2014, 16, 2216.
(20) Yu, Y.; Yang, W.; Pflasterer, D.; Hashmi, A. S. Angew. Chem., Int.
Ed. 2014, 53, 1144.
AUTHOR INFORMATION
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(21) Wang, Z.; Li, L.; Huang, Y. J. Am. Chem. Soc. 2014, 136, 12233.
Corresponding Authors
́
(22) (a) Chinchilla, R.; Najera, C. Chem. Rev. 2007, 107, 874.
Notes
(b) Trost, B. M.; Schmidt, T. J. Am. Chem. Soc. 1988, 110, 2301.
(23) Yu, B.; Xu, W.; Sun, H. M.; Yu, B. X.; Zhang, G. F.; Xu, L.-W.;
Zhang, W. Q.; Gao, Z. W. RSC Adv. 2015, 5, 8351.
(24) Kaminski, Z. J.; Kolesinska, B.; Kolesinska, J.; Sabatino, G.; Chelli,
M.; Rovero, P.; Błaszczyk, M.; Głowka, M. L.; Papini, A. M. J. Am. Chem.
Soc. 2005, 127, 16912.
(25) Jastrzabek, K. G.; Subiros-Funosas, R.; Albericio, F.; Kolesinska,
B.; Kaminski, Z. J. J. Org. Chem. 2011, 76, 4506.
(26) Cai, S.; Yang, K.; Wang, D. Z. Org. Lett. 2014, 16, 2606.
(27) Chuang, D.-W.; El-Shazly, M.; Balaji D, B.; Chung, Y.-M.; Chang,
F.-R.; Wu, Y.-C. Eur. J. Org. Chem. 2012, 2012, 4533.
(28) Kunishima, M.; Hioki, K.; Wada, A.; Kobayashi, H.; Tani, S.
Tetrahedron Lett. 2002, 43, 3323.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported by the 111 Project (B14041),
Innovative Research Team in University of China
(IRT_14R33), National Natural Science Foundation of China
(21171112, 21271124, 21371112, 21446014), Fundamental
Research Funds for the Central Universities (GK201501005,
201503029), Fundamental Doctoral Fund of Ministry of
Education of China (20120202120005), and Shaanxi Innovative
Team of Key Science and Technology (2013KCT-17).
(29) Kaminski, Z. J. Pept. Sci. 2000, 55, 140.
(30) (a) Bao, Y. S.; Chen, C. Y.; Huang, Z. Z. J. Org. Chem. 2012, 77,
8344. (b) Iranpoor, N.; Panahi, F. Adv. Synth. Catal. 2014, 356, 3067.
(31) (a) Satoshi, U.; Eiichiro, M.; Naoto, C.; Kakiuchi, F. J. Am. Chem.
Soc. 2006, 128, 16516. (b) Kirkham, J. D.; Edeson, S. J.; Stokes, S.;
Harrity, J. P. A. Org. Lett. 2012, 14, 5354.
(32) (a) Zhe, L.; Song-L, Z.; Yao, F.; Qing-X, G.; Liu, L. J. Am. Chem.
Soc. 2009, 131, 8815. (b) Kunishima, M.; Ujigawa, T.; Nagaoka, Y.;
Kawachi, C.; Hioki, K.; Shiro, M. Chem.Eur. J. 2012, 18, 15856.
REFERENCES
(1) (a) Tan, G.; Szilva
Chem. Soc. 2014, 136, 9732. (b) Yu, D.-G.; Wang, X.; Zhu, R.-Y.; Luo, S.;
■
́
si, T.; Inoue, S.; Blom, B.; Driess, M. J. Am.
Zhang, X.-B.; Wang, B.-Q.; Wang, L.; Shi, Z.-J. J. Am. Chem. Soc. 2012,
134, 14638.
(2) Quasdorf, K. W.; Tian, X.; Garg, N. K. J. Am. Chem. Soc. 2008, 130,
14422.
D
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