Organic Letters
Letter
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In summary, we have studied an unusual condensation
reaction between formate and acetate esters promoted by the
TiCl4/Et3N system. This methodology has been optimized and
lets one introduce a β-alkoxy- or β-aryloxyacrylate moiety into
acetate esters of different nature. Based on the results, a
mechanism involving a bimetallic intermediate has been
proposed. This reaction increases the knowledge about the
titanium reactivity and could be a basis for future research. The
possible biological activity of these newly synthesized β-alkoxy-
and β-aryloxyacrylates is currently under study.
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Dubey, V. K. Org. Biomol. Chem. 2016, 14, 970−979. (b) Ondet, P.;
̀
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Org. Chem. 2015, 12, 50−54. (d) Burns, M. J.; Ronson, T. O.; Taylor, R.
J. K.; Fairlamb, I. J. S. Beilstein J. Org. Chem. 2014, 10, 1159−1165.
(e) Gharpure, S. J.; Prasath, V. Org. Biomol. Chem. 2014, 12, 7397−7409.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
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S
(f) Palisse, A.; Kirsch, S. F. Eur. J. Org. Chem. 2014, 2014, 7095−7098.
́
(g) Tejedor, D.; Alvarez-Men
́
dez, S. J.; Lop
́
ez-Soria, J. M.; Martín, V. S.;
Experimental details, compound data, and H/13C NMR
1
García-Tellado, F. Eur. J. Org. Chem. 2014, 2014, 198−205. (h) Liu, J.;
Liu, Y. Org. Lett. 2012, 14, 4742−4745.
(6) (a) Cheng, J.-L.; Zhou, Y.; Zhao, J.-H; Zhang, C.; Lin, F.-C. Chin.
Chem. Lett. 2010, 21, 1037−1040. (b) Kerrigan, N. J.; Upadhyay, T.;
Procter, D. J. Tetrahedron Lett. 2004, 45, 9087−9090. (c) Ziegler, T.;
AUTHOR INFORMATION
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Mohler, H.; Effenberger, F. Chem. Ber. 1987, 120, 373−378.
̈
Corresponding Author
ORCID
(7) (a) Andrade, M. M.; Barros, M. T.; Rodrigues, P. Eur. J. Org. Chem.
2007, 2007, 3655−3668. (b) Suda, M. Chem. Lett. 1981, 10, 967−970.
(c) Subramanyam, V.; Silver, E. H.; Soloway, A. H. J. Org. Chem. 1976,
41, 1272−1273.
Notes
(8) Kundu, D.; Maity, P.; Ranu, B. C. Org. Lett. 2014, 16, 1040−1043.
(9) (a) Lapkin, I. I.; Fotin, V. V. Zh. Org. Khim. 1986, 22, 738−743.
(b) Hronowski, L. J. J.; Szarek, W. A. Can. J. Chem. 1985, 63, 2787−
2797.
The authors declare no competing financial interest.
(10) (a) Ciez, D.; Pałasz, A.; Trzewik, B. Eur. J. Org. Chem. 2016, 2016,
̇
ACKNOWLEDGMENTS
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1476−1493 (review about titanium enolate chemistry). (b) Ashida, Y.;
Kajimoto, S.; Nakatsuji, H.; Tanabe, Y. Org. Synth. 2016, 93, 286−305
(mini-review about titanium-promoted Claisen condensation). (c) Na-
katsuji, H.; Nishikado, H.; Ueno, K.; Tanabe, Y. Org. Lett. 2009, 11,
4258−4261 (methodology for α-formylation of esters). (d) Misaki, T.;
Nagase, R.; Matsumoto, K.; Tanabe, Y. J. Am. Chem. Soc. 2005, 127,
2854−2855 (crossed-Claisen condensation). (e) Yoshida, Y.;
Matsumoto, N.; Hamasaki, R.; Tanabe, Y. Tetrahedron Lett. 1999, 40,
4227−4230 (TMSCl as cocatalyst). (f) Yoshida, Y.; Hayashi, R.;
Sumihara, H.; Tanabe, Y. Tetrahedron Lett. 1997, 38, 8727−8730
(TMSOTf as cocatalyst). (g) Matsumura, Y.; Nishimura, M.; Hiu, H.;
Watanabe, M.; Kise, N. J. Org. Chem. 1996, 61, 2809−2812 (first
precedent with TiCl4 as Lewis acid). (h) Tanabe, Y. Bull. Chem. Soc. Jpn.
1989, 62, 1917−1924 (TiCl2(OTf)2 as Lewis acid).
We are grateful to the Ministry of Economy and Competitiveness
of Spain (Project AGL2013-42238-R) and the Junta de
́
Andalucia (FQM-169) for the financial support. J.M.A.-C.
acknowledges the Spanish Ministry of Education, Culture and
Sport for a fellowship. The authors are thankful to the Servicios
́
Centrales de Investigacion
of the University of Cadiz.
́
Cientifica y Tecnolog
́
ica (SC-ICYT)
́
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