HBF4 Catalysed Nucleophilic Substitutions of Propargylic Alcohols
Chem 2009, 1, 342–356; d) R. J. Detz, H. Hiemstra, J. H.
van Maarseveen, Eur. J. Org. Chem. 2009, 6263–6276.
[4] M. N. Pennell, P. G. Turner, T. D. Sheppard, Chem. Eur. J.
2012, 18, 4748–4758.
[5] For a review, see: E. Emer, R. Sinisi, M. G. Capdevila, D. Pe-
truzziello, F. De Vincentis, P. G. Cozzi, Eur. J. Org. Chem. 2011,
647–666.
to be uncovered. For instance, we were pleased to see that
an allylic alcohol also reacted with MeOH at room tem-
perature in very high yields (Scheme 8). Further applica-
tions of this synthetic protocol are currently being investi-
gated in our laboratory.
[6] a) R. Sanz, A. Martínez, J. M. Álvarez-Gutiérrez, F. Rodríg-
uez, Eur. J. Org. Chem. 2006, 1383–1386; b) R. Sanz, D. Mig-
uel, A. Martínez, J. M. Álvarez-Gutiérrez, F. Rodríguez, Org.
Lett. 2007, 9, 727–730; c) R. Sanz, D. Miguel, J. M. Álvarez-
Gutiérrez, F. Rodríguez, Synlett 2008, 975–978; d) R. Sanz,
D. Miguel, A. Martínez, M. Gohain, P. García-García, M. A.
Fernández-Rodríguez, E. Álvarez, F. Rodríguez, Eur. J. Org.
Chem. 2010, 7027–7039.
Scheme 8. Reaction of an allylic alcohol with HBF4.
[7] a) Y. Pan, F. Zheng, H. Lin, Z. Zhan, J. Org. Chem. 2009, 74,
3148–3151; b) Y.-L. Liu, L. Liu, Y.-L. Wang, Y.-C. Han, D.
Wang, Y. J. Chen, Green Chem. 2008, 10, 635–640; c) H.-L.
Yue, W. Wei, M.-M. Li, Y.-R. Yang, J.-X. Ji, Adv. Synth. Catal.
2011, 353, 3159–3145.
[8] a) P. Srihari, J. S. Sunder, D. C. Bhunia, S. S. Mandal, J. S. Ya-
dav, Synth. Commun. 2008, 38, 1448–1455; b) J. S. Yadav,
B. V. S. Reddy, T. Pandurangam, K. V. R. Rao, K. Praneeth,
G. G. K. S. N. Kumar, C. Madavi, A. C. Kunwar, Tetrahedron
Lett. 2008, 49, 4296–4301.
[9] R. Pasceri, H. F. Bartrum, C. J. Hayes, C. J. Moody, Chem.
Commun. 2012, 48, 12077–12079.
[10] M. A. Esteruelas, F. J. Lahoz, A. M. López, E. Oñate, L. A.
Oro, Organometallics 1994, 13, 1669–1678.
Experimental Section
General Procedure for the Nucleophilic Substitution of Propargylic
Alcohols: In a vial fitted with a screw cap and a stirring bar, the
propargylic alcohol 1 (1 mmol), nucleophile (2 mmol) and technical
acetone (2 mL) were introduced. An aqueous solution of HBF4
(48 wt.-%, 1.2 μL,1 mol-%) was then added, and the reaction mix-
ture was stirred at room temperature for 18 h. The reaction was
quenched with a saturated aqueous solution of NaHCO3 and the
mixture extracted with ethyl acetate. The combined organic extracts
were washed with brine, dried with anhydrous MgSO4, filtered, and
concentrated under reduced pressure to give the title compound. If
needed, the crude product was then purified by column chromatog-
raphy.
[11] B. V. S. Reddy, N. S. Reddy, Ch. Madan, J. S. Yadav, Tetrahe-
dron Lett. 2010, 51, 4827–4829.
[12] W. Y. Chen, S. D. Qin, J. R. Jin, Catal. Commun. 2007, 8, 123–
126.
Acknowledgments
[13] V. T. Kamble, B. P. Bandgar, N. S. Joshi, V. S. Jamode, Synlett
2006, 2719–2722.
This research was financially supported by the Imperial College
London and University College London. The Royal Society and
the Engineering and Physical Sciences Research Council (EPSRC)
(EP/K030760/1) are acknoledged for further funding (RG140579).
The Xunta de Galicia (Spain) is acknowledged for a post-doctoral
fellowship to E. B. (I2C plan). A. S. V. thanks the Universidad de
Valencia (Spain) for an Erasmus scholarship. E. T. thanks the Min-
istère de l’Education Nationale et de l’Enseignement Supérieur
(France) and the École Nationale Supérieure de Chimie de Rennes
(ENSCR) for the allocation of a mobility and an Eramus scholar-
ship. LondonCat at ICL and UCL is acknowledged for a summer
studentship to S.-H. L. We thank GlaxoSmithKline (GSK) for sup-
plying the nucleophiles used for the preparation of products 2c–g,
5n and 5q.
[14] D. Stadler, T. Bach, Chem. Asian J. 2008, 3, 272–284.
[15] R. K. Henderson, C. Jiménez-González, D. J. C. Constable,
S. R. Alston, G. G. A. Inglis, G. Fisher, J. Sherwood, S. P.
Binksa, A. D. Curzons, Green Chem. 2011, 13, 854–862.
[16] a) D. A. Engel, G. B. Dudley, Org. Biomol. Chem. 2009, 7,
4149–4158; b) S. Swaminathan, K. V. Narayan, Chem. Rev.
1971, 71, 429–438.
[17] a) M. Bandini, M. Tragni, Org. Biomol. Chem. 2009, 7, 1501–
1507; b) G. A. Olah, Friedel–Crafts Chemistry, Wiley Intersci-
ence, New York, 1973.
[18] R. Sanz, A. Martínez, V. Guilarte, J. M. Álvarez, F. Rodríguez,
Eur. J. Org. Chem. 2007, 4642–4545.
[19] a) J. J. Ritter, P. P. Minieri, J. Am. Chem. Soc. 1948, 70, 4045–
4048; b) J. J. Ritter, J. Kalish, J. Am. Chem. Soc. 1948, 70,
4048–4050.
[20] a) M. Ishikura, K. Yamada, Nat. Prod. Rep. 2009, 26, 803–
852; b) R. J. Sundberg, Indoles, Academic Press, San Diego,
1996.
[21] For a silver-mediated example, see: L. Hao, Y. Pan, T. Wang,
M. Lin, L. Chen, Z.-p. Zhan, Adv. Synth. Catal. 2010, 352,
3215–3222. No conversion was observed in this work when p-
toluenesulfonic acid was tested as catalyst.
[1] D. J. C. Constable, P. J. Dunn, J. D. Hayler, G. R. Humphrey,
J. L. Leazer Jr., R. J. Linderman, K. Lorenz, J. Manley, B. A.
Pearlman, A. Wells, A. Zaks, T. Y. Zhang, Green Chem. 2007,
9, 411–420.
[2] a) R. F. Lochwood, K. M. Nicholas, Tetrahedron Lett. 1977,
18, 4163–4165; b) K. H. Nicholas, Acc. Chem. Res. 1987, 20,
207–214.
[3] For reviews, see: a) Y. Zhu, L. Sun, P. Lu, Y. Wang, ACS Catal.
2014, 4, 1911–1925; b) E. B. Bauer, Synthesis 2012, 44, 1131–
1151; c) Y. Miyake, S. Uemura, Y. Nishibayashi, ChemCat-
[22] a) J. Bergman, S. Högberg, J. Lindström, Tetrahedron 1970, 26,
3347–3351; b) A. H. Jackson, N. Prasitpan, P. V. Shannon,
A. C. Tinker, J. Chem. Soc. Perkin Trans. 1 1987, 2543–2551.
[23] a) X. Zhang, X. Li, J. C. Lanter, Z. Sui, Org. Lett. 2005, 7,
2043–2046. For a review, see: b) E. L. Larghi, T. S. Kaufman,
Synthesis 2006, 187–210.
Received: September 29, 2015
Published Online: October 29, 2015
Eur. J. Org. Chem. 2015, 7544–7549
© 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
7549