Organic Letters
Letter
Scheme 3. Scope of Me3SiCl Mediated Trifluoromethylthio
Lactamization
AUTHOR INFORMATION
Corresponding Author
■
a,b
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
The authors thank the financial support from National Basic
Research Program of China (2012CB821600), National Natural
Science Foundation of China (21172245/21172244/21372247/
21421002) and sioc.
REFERENCES
■
(1) (a) Dowle, M. D.; Davies, D. I. Chem. Soc. Rev. 1979, 8, 171.
(b) Chen, G.-F.; Ma, S. M. Angew. Chem., Int. Ed. 2010, 49, 8306.
(c) Snyder, S. A.; Treitler, D. S.; Brucks, A. P. Aldrichimica Acta 2011, 44,
27. (d) Tan, C.-K.; Zhou, L.; Yeung, Y.-Y. Synlett 2011, 10, 1335.
(e) Denmark, S. E.; Kuester, W. E.; Burk, M. T. Angew. Chem., Int. Ed.
2012, 51, 10938. (f) Nolsoe, J. M. J.; Hansen, T. V. Eur. J. Org. Chem.
2014, 2014, 3051. (g) Cheng, Y.-A.; Yu, W. Z.; Yeung, Y.-Y. Org. Biomol.
Chem. 2014, 12, 2333. (h) Hennecke, U.; Wilking, M. Synlett 2014, 25,
1633.
(2) Ingold, C. K. Structure and Mechanism in Organic Chemistry;
Cornell University Press: Ithaca, 1953; pp 658 − 670.
(3) (a) Capozzi, G.; Modena, G. In Organic Sulfur Chemistry; Bernardi,
F., Csizmadia, I. G., Mangini, A., Eds.; Elsevier: Amsterdam, 1985;
Chapter 5. (b) Smit, V. A.; Zefirov, N. S.; Bodrikov, I. V.; Krimer, M. Z.
Acc. Chem. Res. 1979, 12, 282. (c) Denmark, S. E.; Vogler, T. Chem. - Eur.
J. 2009, 15, 11737.
a
Reaction conditions: compound 4a−h (0.3 mmol), electrophilic
trifluoromethylthiosaccharin (0.45 mmol), Me3SiCl (0.45 mmol) in
(4) Yagupol'skii, L. M.; Ilchenko, A. Y.; Kondratenko, N. V. R. Russ.
Chem. Rev. 1974, 43, 32.
b
CH3CN at room temperature for 3 h. Isolated yields.
(5) (a) Hass, A.; Moller, G. Chem. Ber. 1996, 129, 1383.
̈
(6) (a) Munavalli, S.; Rohrbaugh, D. K.; Rossman, D. I.; Berg, F. J.;
Wagner, G. W.; Durst, H. D. Synth. Commun. 2000, 30, 2847.
(b) Bootwicha, T.; Liu, X.; Pluta, R.; Atodiresei, I.; Rueping, M.
Angew. Chem., Int. Ed. 2013, 52, 12856. (c) Rueping, M.; Liu, X.;
Bootwicha, T.; Pluta, R.; Merkens, C. Chem. Commun. 2014, 50, 2508.
(d) Pluta, R.; Nikolaienko, P.; Rueping, M. Angew. Chem., Int. Ed. 2014,
53, 1650. (e) Kang, K.; Xu, C.-F.; Shen, Q. Org. Chem. Front. 2014, 1,
294. (f) Yang, T.; Lu, L.; Shen, Q. Chem. Commun. 2015, 51, 5479.
(7) Xu, C.-F.; Ma, B.-Q.; Shen, Q. Angew. Chem., Int. Ed. 2014, 53,
9316.
tried many catalysts derived from different chiral Lewis acids, the
best enantioselectivity (23% ee) was observed when a 10 mol %
Et2AlCl/(S)-BINOL was used as the catalyst.10 Clearly, there is
still room for improvement of the enatioselectivity of the
trifluoromethylthio lactonization/lactamization.
(8) (a) Leroux, F.; Jeschke, P.; Schlosser, M. Chem. Rev. 2005, 105, 827.
(b) Manteau, B.; Pazenok, S.; Vors, J.-P.; Leroux, F. R. J. Fluorine Chem.
2010, 131, 140. (c) Boiko, V. N. Beilstein J. Org. Chem. 2010, 6, 880.
(d) Manteau, B.; Pazenok, S.; Vor, J.-P.; Leroux, F. R. J. Fluorine Chem.
2010, 131, 140. (e) Landelle, G.; Panossian, A.; Pazenok, S.; Vors, J.-P.;
Leroux, F. R. Beilstein J. Org. Chem. 2013, 9, 2476. (f) Tlili, A.; Billard, T.
Angew. Chem., Int. Ed. 2013, 52, 6818. (g) Liang, T.; Neumann, C. N.;
Ritter, T. Angew. Chem., Int. Ed. 2013, 52, 8214. (h) He, W.-M.; Weng,
Z.-Q. Prog. Chem. 2013, 25, 1071. (i) Toulgoat, F.; Alazet, S.; Billard, T.
Eur. J. Org. Chem. 2014, 2014, 2415. (j) Xu, X.-H.; Matsuzaki, K.;
Shibata, N. Chem. Rev. 2015, 115, 731. (k) Shao, X.-X.; Xu, C.-F.; Lu, L.;
Shen, Q. Acc. Chem. Res. 2015, 48, 1227.
In summary, we have developed a Lewis acid mediated
trifluoromethylthio lactonization/lactamization of gem-disubsti-
tuted alkenes. The reaction proceeded with excellent selectivity
via an exo-cyclization pathway. It was proposed that a thiiranium
ion intermediate was initially formed, which was further attacked
by the carboxylic acid or amide to generate the corresponding
trifluoromeththiolated lactone/lactam. Further investigation of
the corresponding asymmetric trifluoromethylthio lactoniza-
tion/lactamization is ongoing in our laboratory.
(9) (a) Ferry, A.; Billard, T.; Langlois, B. R.; Bacque, E. Angew. Chem.,
Int. Ed. 2009, 48, 8551. (b) Luo, J.; Zhu, Z.-C.; Liu, Y.-N.; Zhao, X.-D.
Org. Lett. 2015, 17, 3620.
(10) Ishiyama, T.; Ahiko, T.-A.; Miyaura, N. J. Am. Chem. Soc. 2002,
124, 12414.
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
All experimental procedures and spectroscopic data of
compounds 3a−r and 5a−h (PDF)
X-ray crystallography data of 3j (CIF)
C
Org. Lett. XXXX, XXX, XXX−XXX