10.1002/chem.201901219
Chemistry - A European Journal
COMMUNICATION
[16] Y. Ogiwara, D. Sakino, Y. Sakurai, N. Sakai, Eur. J. Org. Chem. 2017,
4324–4327.
stability and reactivity among various kinds of carboxylic acid
derivatives, this reaction can be carried out at moderate reaction
temperatures (80 °C) under an atmosphere of air. At higher
reaction temperatures (180 °C), the decarbonylative coupling of
acyl fluorides proceeds predominantly, resulting in the formation
of the corresponding C–H arylation product. Mechanistic studies
indicated that the cleavage of the aromatic C–H bond, promoted
by a CuX(PPh3) species, is most likely not the rate-limiting step.
In their entirety, the results of this study suggest that acyl fluorides
can potentially be used as versatile building blocks in a wide
variety of C–H bond functionalization reactions.
[17] Y. Ogiwara, Y. Sakurai, H. Hattori, N. Sakai, Org. Lett. 2018, 20, 4204–
4208.
[18] S. T. Keaveney, F. Schoenebeck, Angew. Chem. Int. Ed. 2018, 57,
4073–4077; Angew. Chem. 2018, 130, 4137–4141.
[19] Y. Okuda, J. Xu, T. Ishida, C. Wang, Y. Nishihara, ACS Omega 2018, 3,
13129–13140.
[20] C. A. Malapit, J. R. Bour, C. E. Brigham, M. S. Sanford, Nature 2018,
563, 100–104.
[21] The decarbonylative coupling of aromatic compounds and acyl fluorides
has very recently been reported; see: S. Sakurai, T. Yoshida, M. Tobisu,
Chem. Lett. 2019, 48, 94–97.
[22] Z. Wang, X. Wang, Y. Nishihara, Chem. Commun. 2018, 54, 13969–
13972.
Acknowledgements
[23] T. Scattolin, K. Deckers, F. Schoenebeck, Org. Lett. 2017, 19, 5740–
5743, and references cited therein.
[24] For examples on the acylation of arenes and alkenes using acyl fluorides
(Friedel-Crafts type acylation), see: a) Y. Yamase, Bull. Chem. Soc. Jpn.
1961, 34, 480–484; b) G. A. Olah, M. E. Moffatt, S. J. Kuhn, B. A. Hardie,
J. Am. Chem. Soc. 1964, 86, 2198–2202; c) J. A. Hyatt, P. W. Raynolds,
J. Org. Chem. 1984, 49, 384–385; d) V. G. Nenajdenko, M. V. Lebedev,
E. S. Balenkova, Tetrahedron Lett. 1995, 36, 6317–6320; e) K. V.
Raghavendra Rao, Y. Vallée, Tetrahedron 2016, 72, 4442–4447.
[25] a) X.-F. Wu, P. Anbarasan, H. Neumann, M. Beller, Angew. Chem. Int.
Ed. 2010, 49, 7316–7319; Angew. Chem. 2010, 122, 7474–7477; b) K.
Yang, C. Zhang, P. Wang, Y. Zhang, H. Ge, Chem. Eur. J. 2014, 20,
7241–7244; c) U. K. Sharma, N. Sharma, J. Xu, G. Song, E. V. Van der
Eycken, Chem. Eur. J. 2015, 21, 4908–4912; d) K. Yang, X. Chen, Y.
Wang, W. Li, A. A. Kadi, H.-K. Fun, H. Sun, Y. Zhang, G. Li, H. Lu, J.
Org. Chem. 2015, 80, 11065–11072; e) J. Tjutrins, B. A. Arndtsen, J. Am.
Chem. Soc. 2015, 137, 12050–12054; f) S. Karthik, T. Gandhi, Org. Lett.
2017, 19, 5486–5489.
This work was partially supported by JSPS KAKENHI Grant No.
JP16K21400, a research grant from Central Glass Co., Ltd.
Award in Synthetic Organic Chemistry, Japan, and a research
grant from the Japan Prize Foundation. We acknowledge
Shintaro Hosaka (Tokyo University of Science) for the
experimental assistance on the acyl exchange reaction.
Keywords: homogeneous catalysis • palladium • copper • acyl
fluorides • C–H acylation
[1]
[2]
J. B. Johnson, T. Rovis, Acc. Chem. Res. 2008, 41, 327–338.
L. J. Gooßen, N. Rodríguez, K. Gooßen, Angew. Chem. Int. Ed. 2008,
47, 3100–3120; Angew. Chem. 2008, 120, 3144–3164.
L. J. Gooßen, K. Gooßen, N. Rodríguez, M. Blanchot, C. Linder, B.
Zimmermann, Pure Appl. Chem. 2008, 80, 1725–1733.
M. Blangetti, H. Rosso, C. Prandi, A. Deagostino, P. Venturello,
Molecules 2013, 18, 1188–1213.
[3]
[4]
[26] Even though all reactions were carried out under ambient conditions due
to considerations of practicality, air is not essential for this transformation.
Carrying out the standard reaction under an atmosphere of nitrogen
furnished 3 in 89% GC yield.
[5]
[6]
[7]
[8]
[9]
G. Meng, S. Shi, M. Szostak, Synlett 2016, 27, 2530–2540.
C. Liu, M. Szostak, Chem. Eur. J. 2017, 23, 7157–7173.
J. E. Dander, N. K. Garg, ACS Catal. 2017, 7, 1413–1423.
Y. Gao, C.-L. Ji, X. Hong, Sci. China Chem. 2017, 60, 1413–1424.
R. Takise, K. Muto, J. Yamaguchi, Chem. Soc. Rev. 2017, 46, 5864–
5888.
[27] The DMAP-catalyzed metal-free acylation of azoles by acyl chlorides has
been developed: P. Lassalas, F. Marsais, C. Hoarau, Synlett 2013, 24,
2233–2240. The reaction of azole 1a with acyl fluoride 2a under the
reported conditions did not produce either the acylation product 3 or
decarbonylative coupling product 3’, and the starting substrates 1a and
2a were recovered. The results suggest the higher stability of acyl
fluorides than that of acyl chlorides.
[10] V. Hirschbeck, P. H. Gehrtz, I. Fleischer, Chem. Eur. J. 2018, 24, 7092–
7107.
[11] G. Meng, M. Szostak, Eur. J. Org. Chem. 2018, 2352–2365.
[12] J. Buchspies, M. Szostak, Catalysts 2019, 9, 53–75.
[13] Carboxylic acids are also used in decarbonylative coupling reactions. For
representative reviews on the transition-metal-catalyzed decarbonylative
coupling of carboxylic acid derivatives, see: a) W. I. Dzik, P. P. Lange, L.
J. Gooßen, Chem. Sci. 2012, 3, 2671–2678; b) J. Yamaguchi, K. Muto,
K. Itami, Eur. J. Org. Chem. 2013, 19–30; c) A. Dermenci, G. Dong, Sci.
China Chem. 2013, 56, 685–701; d) L. Guo, M. Rueping, Chem. Eur. J.
2018, 24, 7794–7809; e) C. Liu, M. Szostak, Org. Biomol. Chem. 2018,
16, 7998–8010.
[28] Several other acyl fluorides such as 3-bromopropanoyl fluoride and 3-
nitropropanoyl fluoride were also examined in the acylation of 1a, albeit
that the corresponding ketones were not observed by GC-MS analysis.
[29] The rapid reductive elimination of an acyl C–F bond from palladium(II) at
room temperature has already been reported; see: a) S. L. Fraser, M. Y.
Antipin, V. N. Khroustalyov, V. V. Grushin, J. Am. Chem. Soc. 1997, 119,
4769–4770; b) V. V. Grushin, Chem. Eur. J. 2002, 8, 1006–1014.
[30] The further studies on the acyl exchange reaction are now in progress.
[14] Y. Zhang, T. Rovis, J. Am. Chem. Soc. 2004, 126, 15964–15965.
[15] Y. Ogiwara, Y. Maegawa, D. Sakino, N. Sakai, Chem. Lett. 2016, 45,
790–792.
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