D
E. Yamamoto et al.
Cluster
Synlett
undergo nucleophilic attack by the silyllithium reagent 2,
leading to the formation of the corresponding aryllithium
and silyl halide species. The subsequent nucleophilic sub-
stitution reaction of the aryllithium species with the silyl
halide electrophile would provide the arylsilane product
with concomitant formation of LiBr.
Murakami, K.; Iwasaki, M.; Hirano, K.; Yorimitsu, H.; Koichiro,
O. Bull. Chem. Soc. Jpn. 2009, 82, 1012; and references cited
therein.
(5) For silylation of aryl halides with disilanes, see: (a) Matsumoto,
H.; Nagashima, S.; Yoshihiro, K.; Nagai, Y. J. Organomet. Chem.
1975, 85, C1. (b) Azarian, D.; Dua, S. S.; Eaborn, C.; Walton, D. R.
M. J. Organomet. Chem. 1976, 117, C55. (c) Matsumoto, H.;
Yoshihiro, K.; Nagashima, S.; Watanabe, H.; Nagai, Y.
J. Organomet. Chem. 1977, 128, 409. (d) Matsumoto, H.; Shono,
K.; Nagai, Y. J. Organomet. Chem. 1981, 208, 145. (e) Eaborn, C.;
Griffiths, R. W.; Pidcock, A. J. Organomet. Chem. 1982, 225, 331.
(f) Matsumoto, H.; Kasahara, M.; Matsubara, I.; Takahashi, M.;
Arai, T.; Hasegawa, M.; Nakano, T.; Nagai, Y. J. Organomet. Chem.
1983, 250, 99. (g) Hatanaka, Y.; Hiyama, T. Tetrahedron Lett.
1987, 28, 4715. (h) Babin, P.; Bennetau, B.; Theurig, M.;
Dunoguès, J. J. Organomet. Chem. 1993, 446, 135. (i) Shirakawa,
E.; Kurahashi, T.; Yoshida, H.; Hiyama, T. Chem. Commun. 2000,
1895. (j) Gooßen, L. J.; Ferwanah, A.-R. S. Synlett 2000, 1801.
(k) Denmark, S. E.; Kallemeyn, J. M. Org. Lett. 2003, 5, 3483.
(l) Iwasawa, T.; Komano, T.; Tajima, A.; Tokunaga, M.; Obora, Y.;
Fujihara, T.; Tsuji, Y. Organometallics 2006, 25, 4665.
(m) McNeill, E.; Barder, T. E.; Buchwald, S. L. Org. Lett. 2007, 9,
3785. (n) Minami, Y.; Shimizu, K.; Tsuruoka, C.; Komiyama, T.;
Hiyama, T. Chem. Lett. 2014, 43, 201. (o) Yamamoto, Y.;
Matsubara, H.; Murakami, K.; Yorimitsu, H.; Osuka, A. Chem.
Asian J. 2015, 10, 219. (p) For silylation of aryl halides with silyl-
borane, see: Guo, H.; Chen, X.; Zhao, C.; He, W. Chem. Commun.
2015, 17410.
R
R
R
R
R
R
R
Si Li
R
Si Br
R
Si
Li
LiBr
Br
Scheme 4 A plausible mechanism
In conclusion, we have explored the formal nucleophilic
silyl substitution of aryl and alkenyl halides with silyl nu-
cleophiles. In general, the reaction of aryl bromides with si-
lyl nucleophiles gave the corresponding arylsilanes in mod-
erate to good yields, along with the disilanes. However, ste-
rically hindered aryl halides and substrates bearing an ester
or 3-pyridyl group were not tolerated under the optimized
reaction conditions. The scope of the silyl nucleophile was
also investigated. Mechanistic studies indicated that this re-
action most likely proceeds through a polar halogenophilic
mechanism, as opposed to a radical-mediated mechanism.
(6) (a) Däschlein, C.; Bauer, S. O.; Strohmann, C. Eur. J. Inorg. Chem.
2011, 1454. (b) Strohmann, C.; Bindl, M.; Fraaß, V. C.; Hörnig, J.
Angew. Chem. Int. Ed. 2004, 43, 1011.
Funding Information
(7) For related reactions involved in the halogenophilic attack pro-
cess, see: (a) Mori, M.; Kaneta, N.; Isono, N.; Shibasaki, M. Tetra-
hedron Lett. 1991, 32, 6139. (b) Nagashima, Y.; Takita, R.;
Yoshida, K.; Hirano, K.; Uchiyama, M. J. Am. Chem. Soc. 2013,
135, 18730. (c) Cheung, M. S.; Marder, T. B.; Lin, Z. Organometal-
lics 2011, 30, 3018.
This work was financially supported by the NEXT (Japan) program
(Strategic Molecular and Materials Chemistry through Innovative
Coupling Reactions) of Hokkaido University. This work was also sup-
ported by JSPS KAKENHI Grant Numbers 15H03804, 15K13633, and
26·2447. E.Y. was supported by a Grant-in-Aid for JSPS Fellows.
S
JP
S
K
A
K
E
N
H
I
1(
5
H
0
3
8
0
4SJ)P
S
K
A
K
E
N
H
I
1(
5
K
1
3
6
3
3SJ)P
S
K
A
K
E
N
H
I
2(62·4
4
7)
(8) (a) Yamamoto, E.; Izumi, K.; Horita, Y.; Ito, H. J. Am. Chem. Soc.
2012, 134, 19997. (b) Yamamoto, E.; Ukigai, S.; Ito, H. Chem. Sci.
2015, 6, 2943. (c) Uematsu, R.; Yamamoto, E.; Maeda, S.; Ito, H.;
Taketsugu, T. J. Am. Chem. Soc. 2015, 137, 4090.
Supporting Information
Supporting information for this article is available online at
(9) (a) Kawachi, A.; Minamimoto, T.; Tamao, K. Chem. Lett. 2001, 30,
1216. (b) Hata, T.; Kitagawa, H.; Masai, H.; Kurahashi, T.;
Shimizu, M.; Hiyama, T. Angew. Chem. Int. Ed. 2001, 40, 790.
(c) O’Brien, J. M.; Hoveyda, A. H. J. Am. Chem. Soc. 2011, 133,
7712. (d) Ito, H.; Horita, Y.; Yamamoto, E. Chem. Commun. 2012,
8006. (e) Oshima, K.; Ohmura, T.; Suginome, M. Chem. Commun.
2012, 8571. (f) Kleeberg, C.; Borner, C. Eur. J. Inorg. Chem. 2013,
2799. (g) Shintani, R.; Fujie, R.; Takeda, M.; Nozaki, K. Angew.
Chem. Int. Ed. 2014, 53, 6546. (h) Nagao, K.; Ohmiya, H.;
Sawamura, M. Org. Lett. 2015, 17, 1304. (i) Wu, H.; Garcia, J. M.;
Haeffner, F.; Radomkit, S.; Zhugralin, A. R.; Hoveyda, A. H. J. Am.
Chem. Soc. 2015, 137, 10585. For reviews, see: (j) Oestreich, M.;
Hartmann, E.; Mewald, M. Chem. Rev. 2013, 402. (k) Cuenca, A.
B.; Shishido, R.; Ito, H.; Fernández, E. Chem. Soc. Rev. 2017, 46,
415.
S
u
p
p
ortioInfgrmoaitn
S
u
p
p
ortiInfogrmoaitn
References and Notes
(1) New address: Department of Chemistry, Graduate School of Sci-
ence, Kyushu University, Motooka 477, Nishi-ku, Fukuoka 819-
0395, Japan.
(2) (a) Showell, G. A.; Mills, J. S. Drug Discovery Today 2003, 8, 551.
(b) You, Y.; An, C.-G.; Kim, J.-J.; Park, S. Y. J. Org. Chem. 2007, 72,
6241. (c) Liu, X.-M.; He, C.; Huang, J.; Xu, J. Chem. Mater. 2005,
17, 434. (d) Denmark, S. E.; Ober, M. H. Aldrichimica Acta 2003,
36, 75.
(3) For reviews see: (a) Brook, M. A. In Silicon in Organic, Organome-
tallic, and Polymer Chemistry; Wiley-Interscience: New York,
2000, 1st ed. 115. (b) Hiyama, T. In Organometallics in Synthesis
Third Manual; Schlosser, M., Ed.; Wiley: Hoboken, 2013, 373.
(4) (a) Murakami, K.; Hirano, K.; Yorimitsu, H.; Oshima, K. Angew.
Chem. Int. Ed. 2008, 47, 5833. (b) Murakami, K.; Yorimitsu, H.;
Oshima, K. J. Org. Chem. 2009, 74, 1415. (c) Morita, E.;
(10) Abeywickrema, A. N.; Beckwith, A. L. J. J. Chem. Soc., Chem.
Commun. 1986, 464.
(11) Typical Procedure for Silyl Substitution Reaction with Silyl-
lithium Reagent
A vial with a screw cap and a silicon-coated rubber septum was
connected to a vacuum/nitrogen manifold through a needle,
and it was evacuated and refilled with nitrogen three times.
© Georg Thieme Verlag Stuttgart · New York — Synlett 2017, 28, A–E