10.1002/anie.201808646
Angewandte Chemie International Edition
COMMUNICATION
D. R. M. Walton, J. Organomet. Chem. 1976, 117, C55; (c) H. Matsumoto,
K. Yoshihiro, S. Nagashima, H. Watanabe, Y. Nagai, J. Organomet.
Chem. 1977, 128, 409; (d) H. Matsumoto, K. Shono, Y. Nagai, J.
Organomet. Chem. 1981, 208, 145; (e) C. Eaborn, R. W. Griffiths, A.
Pidcock, J. Organomet. Chem. 1982, 225, 331; (f) H. Matsumoto, M.
Kasahara, I. Matsubara, M. Takahashi, T. Arai, M. Hasegawa, T. Nakano,
Y. Nagai, J. Organomet. Chem. 1983, 250, 99; (g) Y. Hatanaka, T.
Hiyama, Tetrahedron Lett. 1987, 28, 4715; (h) P. Babin, B. Bennetau, M.
Theurig, J. Dunoguès, J. Organomet. Chem. 1993, 446, 135; (i) E.
Shirakawa, T. Kurahashi, H. Yoshida, T. Hiyama, Chem. Commun. 2000,
1895; (j) L. J. Gooßen, A.-R. S. Ferwanah, Synlett 2000, 1801; (k) S. E.
Denmark, J. M. Kallemeyn, Org. Lett. 2003, 5, 3483; (l) T. Iwasawa, T.
Komano, A. Tajima, M. Tokunaga, Y. Obora, T. Fujihara, Y. Tsuji,
Organometallics 2006, 25, 4665; (m) E. McNeill, T. E. Barder, S. L.
Buchwald, Org. Lett. 2007, 9, 3785; (n) Y. Minami, K. Shimizu, C.
Tsuruoka, T. Komiyama, T. Hiyama, Chem. Lett. 2014, 43, 201; (o) Y.
Yamamoto, H. Matsubara, K. Murakami, H. Yorimitsu, A. Osuka, Chem.
Asian J. 2015, 10, 219; (p) With silyl-boranes: H. Guo, X. Chen, C. Zhao,
W. He, Chem. Commun. 2015, 17410.
yields offering a novel approach to silylated arenes. Theoretical
studies showed that these transformations occur by a concerted
nucleophilic aromatic substitution via
a
4-membered
asynchronous transition state. In contrast to nucleophilic aromatic
substitutions the herein disclosed reaction also occurs on
electron-rich fluoroarenes. We further found that ortho-
deprotonation of the fluoroarene by PhMe2SiLi leading to the
corresponding aryne can compete with the concerted ipso-
substitution in selected cases. The ipso-substitution was
successfully applied to a novel synthesis of 9-silafluorenes.
Acknowledgements
This work was supported by the Westfälische Wilhelms-University
Münster (PhD fellowship to Shubhadip Mallick) and the China
Scholarship Council (stipend to Pan Xu).
[7]
(a) A. G. Brook, S. Wolfe. J. Am. Chem. Soc. 1957, 79, 1431; (b) H.
Gilman, G. D. Lichtenwalter, J. Am. Chem. Soc. 1958, 80, 608; (c) D. P.
Dervan, M. A. Shippey, J. Am. Chem. Soc. 1976, 98, 1265; (d) S. Saito,
K. Shimada, H. Yamamoto, E. M. D. Marigorta, I. Fleming, Chem.
Commun. 1997, 1299.
Keywords: aromatic substitution • DFT calculations • fluoride •
transition-metal-free • silylation
[8]
[9]
(a) C. Däschlein, S. O. Bauer, C. Strohmann, Eur. J. Inorg. Chem. 2011,
1454; (b) E. Yamamoto, S. Ukigai, H. Ito, Synlett 2017, 28, 2460.
P. Xu, E.-U. Würthwein, C. G. Daniliuc, A. Studer, Angew. Chem. 2017,
129,14060, Angew. Chem. Int. Ed. 2017, 56, 13872.
[1]
(a) F. Terrier, Modern Nucleophilic Aromatic Substitution, Wiley-VCH,
Weinheim, Germany, 2013; (b) K. Blaziak, W. Danikiewicz, M. Makosza,
J. Am. Chem. Soc. 2016, 138, 7276 and references cited therein.
A. Bhunia, S. R. Yetra, A. T. Biju, Chem. Soc. Rev. 2012, 41, 3140 and
references cited therein.
[2]
[3]
[10] C. Hansch, A. Leo, R. W. Taft, Chem. Rev. 1991, 91, 165.
[11] (a) M. Shimizu, T. Hiyama, T. Synlett 2012, 23, 973; (b) J. Y. Corey, Adv.
Organometal. Chem. 2011, 59, 181.
(a) J. Shakes; C. Raymond, D. Rettura, A. Williams, J. Chem. Soc.,
Perkin Trans. 2 1996, 1553; (b) N. R. Cullum, D. Rettura, J. M. J.
Whitmore, A. Williams, J. Chem. Soc., Perkin Trans. 2 1996, 1559; (c) L.
I. Goryunov, J. Grobe, V. D. Shteingarts, B. Krebs, A. Lindemann, E.-U.
Würthwein, C. Mück-Lichtenfeld, Chem. Eur. J. 2000, 6, 4612; (d) X. Liu,
J. Warkentin, Can. J. Chem. 2001, 79, 364; (e) G. C. Lloyd-Jones, J. D.
Moseley, J. S. Renny, Synthesis 2008, 661; (f) L. I. Goryunov, J. Grobe,
D. Le Van, V. D. Shteingarts, R. Mews, E. Lork, E.-U. Würthwein, Eur. J.
Org. Chem. 2010, 1111; (g) K. Tomohara, T. Yoshimura, R. Hyakutake,
P. Yang, T. Kawabata, J. Am. Chem. Soc. 2013, 135, 13294; (h) S. I.
Zhivetyeva, L. I. Goryunov, I. Yu. Bagryanskaya, J. Grobe, V. D.
Shteingarts, E.-U. Würthwein, J. Fluorine Chem. 2014, 164, 58; (i) R. C.
Atkinson, F. Fernández-Nieto, J. M. Roselló, J. Clayden, Angew. Chem.
2017, 127, 9089; Angew. Chem. Int. Ed. 2015, 54, 8961; (j) C. N.
Neumann, J. M. Hooker, T. Ritter, Nature 2016, 534, 369; (k) A. Kaga, H.
Hayashi, H. Hakamata, M. Oi, M. Uchiyama, R. Takita, S. Chiba, Angew.
Chem. 2017, 129, 11969; Angew. Chem. Int. Ed. 2017, 56, 11807; (l) R.
Costil, H. J. A. Dale, N. Fey, G. Whicombe, J. V. Matlock, J. Clayden,
Angew. Chem. 2017, 129, 12707; Angew. Chem. Int. Ed. 2017,
56,12533; (m) K. Kikushima, M. Grellier, M. Ohashi, S. Ogoshi, Angew.
Chem. 2017, 129, 16409, Angew. Chem. Int. Ed. 2017, 56, 16191; (n) S.
D. Schimler, M. A. Cismesia, P. S. Hanley, R. D. J. Froese, M. J. Jansma,
D. C. Bland, M. S. Sanford, J. Am. Chem. Soc. 2017, 139, 1452; (o) G.
J. P. Perry, J. M. Quibell, A. Panigrahi, I. Larossa, J. Am. Chem. Soc.
2017, 139, 11527; (p) C. N. Neumann, T. Ritter, Acc. Chem. Res. 2017,
50, 2822; (q) J. M. Quibell, G. J. P. Perry, D. M. Cannas, I. Larossa,
Chem. Sci. 2018, 9, 3860; (r) E. E. Kwan, Y. Zeng, H. A. Besser, E. N.
Jacobsen, Nature Chem. 2018, 10, 917; (s) D. J. Leonard, J. W. Ward,
J. Clayden, Nature 2018, 562, 105.
[12] Transition-metal free synthesis of 9-silafluorenes from ortho-
silylbiphenyls, see: (a) D. Leifert, A. Studer, Org. Lett. 2015, 17, 386; (b)
L. Xu, S. Zhang, P. Li, Org. Chem. Front. 2015, 2, 459.
[13] (a) A. A. Toutov, W.-B. Liu, K. N. Betz, A. Fedorov, B. M. Stoltz, R. H.
Grubbs, Science 2015, 518, 80; (b) W.-B. Liu, D. P. Schuman, Y. F. Yang,
A. A. Toutov, Y. Liang, H. F. T. Klare, N. Nesnas, M. Oestreich, D. G.
Blackmond, S. C. Virgil, S. Banerjee, R. N. Zare, R. H. Grubbs, K. N.
Houk, B. M. Stoltz, J. Am. Chem. Soc. 2017, 139, 6867; (c) S. Banerjee,
Y.-F. Yang, I. D. Jenkins, Y. Liang, A. A. Toutov, W.-B. Liu, D. P.
Schuman, R. B. Grubbs, B. M. Stoltz, E. H. Krenske, K. N. Houk, R. N.
Zare, J. Am. Chem. Soc. 2017, 139, 6880.
[4]
[5]
(a) M. G. Steinmetz, Chem. Rev. 1995, 95, 1527; (b) M. Weidenbruch,
Chem. Rev. 1995, 95, 1479; (c) A. Hosomi, K. Miura, Bull. Chem. Soc.
Jpn. 2004, 77, 835.
(a) Science of Synthesis, Vol. 4 (Ed.: I. Fleming), Thieme, Stuttgart, 2002,
Chapter 4.4; (b) M. A. Brook, Silicon in Organic, Organometallic, and
Polymer Chemistry, Wiley, New York, 2000, Chapter 5; (c) L. Birkofer, O.
Stuhl, The Chemistry of Organic Silicon Compounds (Eds.: S. Patai, Z.
Rappoport), Wiley, New York, 1989, Chapter 10.
[6]
With disilanes: (a) H. Matsumoto, S. Nagashima, K. Yoshihiro, Y. Nagai,
J. Organomet. Chem. 1975, 85, C1; (b) D. Azarian, S. S. Dua, C. Eaborn,
This article is protected by copyright. All rights reserved.