Malaysian Journal of Chemistry, 2017, Vol. 19(1), 13–23

FeCl3/ AgOTf Catalyzed Hydroarylation Reactions of Aryl-substituted
Alkynes with Different Electron-rich Arenes

Md. Ataur Rahman1* and Tsugio Kitamura2
1Department of Chemistry, Jahangirnagar University, Savar, Dhaka-1342, Bangladesh.
2Department of Chemistry and Applied Chemistry, Graduate School of Science and Engineering, Saga University, Honjo-machi, Saga, 840-8502, Japan.

*Corresponding author (e-mail: This email address is being protected from spambots. You need JavaScript enabled to view it.)

 Received: June 2016; Accepted: January 2017


There are many synthetic methods for the direct formation of carbon-carbon bond between arenes and alkynes. Metal-catalyzed hydroarylation reaction is one of the synthetic methods for the direct formation of new carbon-carbon bond between arenes and alkynes. The hydroarylation reaction of aryl-substituted alkynes with arenes proceeded smoothly in the presence of FeCl3/AgOTf catalyst system in a mixed solvent of trifluoroacetic acid and dichloromethane at 30ºC and yielded aryl-substituted alkenes in moderate to high yields. Electron rich arenes gave high yields whereas the relatively less electron rich arenes gave norminal yields. 

Key words: FeCl3/AgOTf catalyst; hydroarylation; alkynes; arenes; arylalkenes


Fujiwara, Y. and Kitamura, T. (2005) Handbook of C-H transformations, ed. Dyker, G., Wiley-VCH, Weinheim.

Kakiuchi, F. and Murai, S. (1999) Activation of unreactive bonds and organic synthesis, ed. Murai, S., Springer, Berlin.

Shilov, A.E. and Shul’pin, G.B. (1997) Activation of C−H bonds by metal complexes, Chemical Reviews, 97(8), 2879–2932.

Trost, B.M. (1991) The atom economy--a search for synthetic efficiency, Science, 254 (5037), 1471–1477.

Diederich, F. and de Meijere, A. (2004) Metal-catalyzed cross-coupling reactions, 2nd edn. Wiley-VCH, New York, NY, USA.

Miyaura, N. (2002) Cross-coupling reactions: a practical guide, Springer, Berlin, Germany.

Diederich, F. and Stang, P.J. (1998) Metal-catalyzed cross-coupling reactions, Wiley-VCH, New York, NY, USA.

Carey, F.A. and Sundberg, R.J. (2001) Advanced organic chemistry, Part B, 4th edn., Kluwer Academic / Plenum Press, New York, chap. 11.

Smith, M.B. and March, J. (2007) March’s advanced organic chemistry, 6th edn. Wiley Interscience, New York, chap. 11.

Ullmann, F. and Bielecki, J. (1901) Ueber synthesen in der biphenylreihe, Berichte der Deutschen Chemischen Gesellschaft, 34(2), 2174–2185.

Rahman, M.A. Ogawa, O. Oyamada, J. and Kitamura, T. (2008) Metal-free hydroarylation of alkynes: a very convenient, simple procedure for substituted arylalkenes, Synthesis, 3755–3760.

Corson, B.B. Dorsky, J. Nickels, J.E. Kutz, W. M. and Thayer, H.I. (1954) Dimerization of styrene in the presence and absence of solvent, Journal of Organic Chemistry, 19, 17–26.

Kitamura, T. (2009) Transition-metal-catalyzed hydroarylation reactions of alkynes through direct functionalization of C–H bonds: A convenient tool for organic synthesis, European Journal of Inorganic Chemistry, 1111–1125.

Biffis, A. Gazzola, L. Gobbo, P. Buscemi, G. Tubaro, C. and Basato, M. (2009) Alkyne hydroarylations with chelating dicarbene palladium (II) complex catalysts: Improved and unexpected reactivity patterns disclosed upon additive screening, European Journal of Inorganic Chemistry, 3189–3198.

Kakiuchi, F. and Chatnai, N. (2003) Catalytic methods for C–H bond functionalization: Application in organic synthesis, Advanced Synthesis & Catalysis, 345, 1077–1101.

Ritleng, V. Sirlin, C. and Pfeffer, M. (2002) Ru-, Rh-, and Pd-catalyzed C–C bond formation involving C–H activation and addition on unsaturated substrates: reactions and mechanistic aspects, Chemical Reviews, 102(5), 1731–1770.

Jia, C. Kitamura, T. and Fujiwara,Y. (2001) Catalytic functionalization of arenes and alkanes via C–H bond activation, Accounts of Chemical Research, 34(8), 633–639.

Crabtree, R.H. (2001) Alkane C–H activation and functionalization with homogeneous transition metal catalysts: A century of progress—a new millennium in prospect, Journal of the Chemical Society, Dalton Transactions, 2437–2450.

Jia, C. Lu, W. Oyamada, J. Kitamura, T. Matsuda, K. Irie, M. and Fujiwara, Y. (2000) Novel Pd(II)- and Pt(II)-catalyzed regio- and stereoselective trans-hydroarylation of alkynes by simple arenes, Journal of the American Chemical Society, 122(30), 7252–7263.

Guari, Y. Sabo- Etienne, S. and Chaudret, B. (1999) Catalytic formation of carbon–carbon bonds by activation of carbon–hydrogen bonds, European Journal of Inorganic Chemistry, 1047–1055.

Ming-Chang, P.Y. Yuan-shin, S. Hsin-Hui, L. Tzu-Yu, Y. Ting-Chia, H. and Jia-Jyun, H. (2016) Iron (II) halide promoted cyclization of cyclic 2-enynamides: Stereoselective synthesis of halogenated bicyclic γ-lactams, Organic Letters, 18(10), 2407–2410.

Ingmar, B. and Hans-Joachim, K. (2015) Iron catalysis in organic synthesis, Chemical Reviews, 115(9), 3170–3387.

Viciu, M.S. Stevens, E.W. Petersen, J.L. and Nolan, S.P. (2004) N-Heterocyclic carbene palladium complexes bearing carboxylate ligands and their catalytic activity in the hydroarylation of alkynes, Organometallics, 23(15), 3752–3755.

Reetz, M.T. and Sommer, K. (2003) Gold-catalyzed hydroarylation of alkynes, European Journal of Organic Chemistry, 3485–3496.

Kischel, J. Jovel, I. Mertins, K. Zapf, A and Beller, M. (2006) A convenient FeCl3-catalyzed hydroarylation of styrenes, Organic Letters, 8(1),19–22.

Komeyama, K. Morimoto, T. and Takaki, K. (2006) A simple and efficient iron-catalyzed intramolecular hydroamination of unactivated olefins, Angewandte Chemie International Edition, 45(18), 2938–2941.

Iovel, I. Mertins, K. Kischel, J. Zapf, A. and Beller, M. (2005) An efficient and general iron-catalyzed arylation of benzyl alcohols and benzyl carboxylates, Angewandte Chemie International Edition, 44(25), 3913–3917.

Nakamura, M. Hirai, A. and Nakamura, E. (2000) Iron-catalyzed olefin carbometalation, Journal of the American Chemical Society, 122(5), 978–979.

Bolm, C. Legros, J. Paih, J. and Zani, L. (2004) Iron-catalyzed reactions in organic synthesis, Chemical Reviews, 104(12), 6217–6254.

Li, R. Wang, S.R. and Lu, W. (2007) FeCl3-Catalyzed alkenylation of simple arenes with aryl-substituted alkynes, Organic Letters, 9(11), 2219–2222.

Komeyama, K. Igawa, R. and Takaki, K. (2010) Cationic iron-catalyzed intramolecular alkyne-hydroarylation with electron-deficient arenes, Chemical communications, 46, 1748–1750.

Hashimoto, T. Izumi, T. Kutubi, M. S. and Kitamura, T. (2010) Iron(III)-catalyzed hydroarylation of propiolic acid with activated arenes, Tetrahedron Letters, 51(4), 761-763.

Hashimoto, T. Kutubi, S. Izumi, T. Rahman, A. and Kitamura, T. (2011) Catalytic hydroarylation of alkynes with arenes in the presence of FeCl3 and AgOTf, Journal of Organometallic Chemistry, 696(1), 99–105.

Tsuchimoto, T. Maeda, T. Shirakawa, E. and Kawakami, Y. (2000) Friedel–Crafts alkenylation of arenes using alkynes catalysed by metal trifluoromethanesulfonates, Chemical Communications (Cambridge), 1573–1574.

View Full Article
back to top