10.1002/anie.201803647
Angewandte Chemie International Edition
COMMUNICATION
to give the desired tricarbanion after deprotonation. Studies to
clarify this are currently underway.
137, 232-238; d) L. Feng, et al., J. Am. Chem. Soc. 2006, 128, 5990-
5991.
[5]
[6]
[7]
R. Noyori, I. Nishida, J. Sakata, J. Am. Chem. Soc. 1983, 105, 1598-
1608.
In conclusion, although tetraalkylammonium ions are only
weakly coordinating cations and as such provide limited
electrostatic stabilization, the formation of a purely organic
tricarbanion salt has been observed for the first time. Our results
showcase the exceptional anion stabilizing ability of triflyl groups
which we consider essential for the formation of stable highly
charged anionic species, opening the possibility of the formation
of organic polycarbanions.
M. T. Reetz, S. Hütte, R. Goddard, J. Am. Chem. Soc. 1993, 115, 9339-
9340.
a) M. B. Smith, J. March, in March's Advanced Organic Chemistry, 3rd
ed., John Wiley & Sons, Inc., 2006, pp. 320-322; b) C. M. Starks, J. Am.
Chem. Soc. 1971, 93, 195-199.
[8]
[9]
a) I. Kuwajima, E. Nakamura, J. Am. Chem. Soc. 1975, 97, 3257-3258;
b) I. Kuwajima, E. Nakamura, Acc. Chem. Res. 1985, 18, 181-187.
a) C. Hansch, A. Leo, R. W. Taft, Chem. Rev. 1991, 91, 165-195; b) D.
Höfler, M. van Gemmeren, P. Wedemann, K. Kaupmees, I. Leito, M.
Leutzsch, J. B. Lingnau, B. List, Angew. Chem. Int. Ed. 2017, 56, 1411-
1415; c) L. Turowsky, K. Seppelt, Inorg. Chem. 1988, 27, 2135-2137.
Acknowledgements
Generous support by the Max-Planck-Society, the Deutsche
Forschungsgemeinschaft (Leibniz Award to B.L. and Cluster of
Excellence RESOLV, EXC 1069), and the European Research
Council (Advanced Grant “C–H Acids for Organic Synthesis,
CHAOS”) is gratefully acknowledged. R.G. thanks J. Breidung
for helpful discussions. We thank the members of our analytical
departments for their excellent service.
[10] Z. Arnold, M. Budesinsky, J. Org. Chem. 1988, 53, 5352-5353.
[11] Please see reference [16] for crystal data.
[12] a) K. Kuchitsu, T. Fukuyama, Y. Morino, J. Mol. Struct. 1968, 1, 463-
479; b) T. S. Thakur, M. T. Kirchner, D. Bläser, R. Boese, G. R.
Desiraju, Phys. Chem. Chem. Phys. 2011, 13, 14076-14091.
[13] S. P. Thomas, M. W. Shi, G. A. Koutsantonis, D. Jayatilaka, A. J.
Edwards, M. A. Spackman, Angew. Chem. Int. Ed. 2017, 56, 8468-
8472.
Keywords: tetraalkylammonium cation
•
purely organic
tricarbanion • highly charged anion • triflyl stabilization
[14] M. S. Schmøkel, S. Cenedese, J. Overgaard, M. R. V. Jørgensen, Y.-S.
Chen, C. Gatti, D. Stalke, B. B. Iversen, Inorg. Chem. 2012, 51, 8607-
8616.
[1]
a) A. Hasegawa, T. Ishikawa, K. Ishihara, H. Yamamoto, Bull. Chem.
Soc. Jpn. 2005, 78, 1401-1410; b) J. Lu, T. H. Le, D. A. K. Traore, M.
Wilce, A. M. Bond, L. L. Martin, J. Org. Chem. 2012, 77, 10568-10574;
c) T. Mitsuhashi, M. Goto, K. Honda, Y. Maruyama, T. Inabe, T.
Sugawara, T. Watanabe, Bull. Chem. Soc. Jpn. 1988, 61, 261-269.
D. J. Cram, Fundamentals of carbanion chemistry, Vol. 4, Elsevier,
2012.
[15] a) H. Yanai, S. Egawa, T. Taguchi, Tetrahedron Lett. 2013, 54, 2160-
2163; b) H. Yanai, H. Ogura, H. Fukaya, A. Kotani, F. Kusu, T. Taguchi,
Chemistry 2011, 17, 11747-11751.
[16] The crystal structure of 1: C38H65Cl2F18N3O13S6, Mr = 1377.19 g.mol-1,
colourless prism, monoclinic, P21/c (no. 14), a = 11.372(2) Å, b =
45.769(8) Å, c = 12.482(2) Å, β = 115.053(3)°, V = 5885.3(17) Å3, T =
100(2) K, Z = 4, dcalcd = 1.554 Mgm-3, Mo-Kα radiation, λ = 0.71073 Å.
Further details of the crystal structure analysis are given in the
Supporting Information. CCDC-1824208.
[2]
[3]
[4]
B. List, Acc. Chem. Res. 2004, 37, 548-557.
a) A. S. Filatov, A. V. Zabula, S. N. Spisak, A. Y. Rogachev, M. A.
Petrukhina, Angew. Chem. Int. Ed. 2014, 53, 140-145; b) A. V. Zabula,
A. S. Filatov, S. N. Spisak, A. Y. Rogachev, M. A. Petrukhina, Science
2011, 333, 1008-1011; c) M. Yamada, et al., J. Am. Chem. Soc. 2015,
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