Categories: C-Si Bond Formation > Silanes
Synthesis of arylsilanes
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A zinc-catalyzed nucleophilic substitution reaction of chlorosilanes with
organomagnesium reagents affords a broad range of functionalized
tetraorganosilanes under mild reaction conditions. The reaction can be performed
on large scale.
K. Murakami, H. Yorimitsu, K. Oshima, J. Org. Chem., 2009,
74, 1415-1417.
Various siletanes have been used as substrates for the oxidation of
carbon-silicon bonds upon exposure to aqueous fluoride and peroxide. These
tetraalkylsilanes offer a combination of stability and reactivity with many
practical benefits, including compatibility with silicon protecting groups
and electron-rich aromatic rings.
J. D. Sunderhaus, H. Lam, G. B. Dudley, Org. Lett.,
2003, 8, 4571-4573.
Rapid, efficient methods enable the preparation of phenols from the
oxidation of arylhydrosilanes. Electron-rich aromatics benefit from
silane activation via oxidation to the methoxysilane using homogeneous or
heterogeneous transition metal catalysis. A combination of these two
oxidations into a streamlined flow procedure involves minimal processing of
reaction intermediates.
E. J. Rayment, N. Summerhill, E. A. Anderson, J. Org. Chem., 2012,
77, 7052-7060.
A new palladium-catalyzed silylation of aryl chlorides affords desired product
in good yield, is tolerant of various functional groups, and provides access to
a wide variety of aryltrimethylsilanes from commercially available aryl
chlorides. Additionally, a one-pot procedure that converts aryl chlorides into
aryl iodides has been developed.
E. McNeill, T. E. Barder, S. L. Buchwald, Org. Lett., 2007,
9, 3785-3788.
A Ni/Cu-catalyzed silylation of unactivated C-O electrophiles derived from
phenols or benzyl alcohols offers a wide scope and mild conditions and provides
a direct access to synthetically versatile silylated compounds.
C. Zarate, R. Martin, J. Am. Chem. Soc., 2014,
136, 2236-2239.
An iron-catalyzed method for the silylation of (hetero)aromatic chlorides
features high efficiency, a broad substrate scope, and excellent functional
group compatibility. Moreover, this protocol enables the late-stage silylation
of some pharmaceuticals.
J. Jia, X. Zeng, Z. Liu, L. Zhao, C.-Y. He, X.-F. Li, Z. Feng,
Org. Lett., 2020, 22, 2816-2821.
A base-mediated borylsilylation of benzylic ammonium salts provides geminal
silylboronates bearing benzylic proton under mild reaction conditions.
Deaminative silylation of aryl ammonium salts was also achieved in the presence
of LiOtBu. Both methods offer high efficiency, mild reaction conditions,
and good functional group tolerance for late-stage functionalization of amines.
W.-Y. Qi, J.-S. Zhen, X.-h. Xu, X. Du, Y.-h. Li, H. Yuan, Y.-S. Guan, X. Wei,
Z.-Y. Wang, G. Liang, Y. Luo, Org. Lett., 2021, 23,
5988-5992.
An efficient palladium-catalyzed silylation of activated aryl and alkenyl
ketones offers high efficiency and broad substrate scope. Further applications
in the late-stage diversification of biologically important molecules
demonstrate the synthetic utility of this method.
X. Wang, Z.-Y. Wang, X. Zhang, H. Xu, H.-X. Dai, Org. Lett.,
2022, 24, 7344-7349.
An unprecedented nickel-catalyzed decarbonylative silylation of silyl ketones
provides structurally diverse arylsilanes under mild reaction conditions.
W. Srimontree, W. Lakornwong, M. Rueping,
Org. Lett., 2019, 21, 9330-9333.
By treatment with s-BuLi/TMEDA at -78°C, unprotected 2-methoxybenzoic
acid is deprotonated exclusively in the position ortho to the
carboxylate. A reversal of regioselectivity is observed when the acid is
treated with n-BuLi/t-BuOK.
T.-H. Nguyen, A.-S. Castanet, J. Mortier, Org. Lett.,
2006, 8, 765-768.
Related
Treatment of substituted arylbromides with tert-butyllithium in diethyl
ether at -78˚C, followed by the addition to dichlorodiethoxysilane, leads to the
quantitative formation of diaryldiethoxysilanes. Diaryldiethoxysilanes can be
reduced to the corresponding diarylsilanes by stirring with lithium aluminum
hydride in diethyl ether. This method avoids the handling of gaseous and
explosive dichlorosilane.
P. Gigier, W. A. Herrmann, F. E. Kühn, Synthesis, 2010,
1431-1432.