Categories: C-Si Bond Formation > Silanes
Synthesis of vinylsilanes
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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.
The nickel-catalyzed reaction of terminal alkenes with silacyclobutanes afforded
the corresponding vinylsilanes in a highly regio- and stereoselective fashion.
The reaction provides a facile access to vinylsilanes starting from trivial
terminal alkenes as well as styrenes, 1,3-dienes, and acrylate esters.
K. Hirano, H. Yorimitsu, K. Oshima, J. Am. Chem. Soc., 2007,
129, 6094-6095.
A complex of [Ir(OMe)(cod)]2 and 4,4-di-tert-butyl-2,2-bipyridine
(dtbpy) catalyzes the Z-selective, dehydrogenative silylation of terminal
alkenes, but not internal alkenes, with triethylsilane or benzyldimethylsilane
in THF. Yields and Z-stereoselectivity were significantly improved by
2-norbornene as sacrificial alkene. The reaction tolerates many functional
groups.
B. Lu, J. R. Falck, J. Org. Chem., 2010,
75, 1701-1705.
Grubbs' first-generation Ru metathesis complex catalyses the hydrosilylation of terminal alkynes. The reaction exhibits an interesting selectivity profile that is dependent on the reaction concentration and more importantly on the silane employed.
C. S. Arico, L. R. Cox, Org. Biomol. Chem., 2004, 2, 2558-2562.
Copper(I) catalyzes a highly regioselective synthesis of branched vinylsilanes
through silicon-copper additions to terminal alkynes using methanol as additive.
The corresponding vinylsilanes were obtained with excellent branched to linear
selectivity in good yields.
P. Wang, X.-L. Yeo, T.-P. Loh, J. Am. Chem. Soc., 2011,
133, 1254-1256.
A highly regio- and stereoselective palladium-catalyzed synthesis of various
2-silylallylboronates from allenes and
2-(dimethylphenylsilanyl)-4,4,5,5-tetramethyl[1,3,2]dioxaborolane afforded the
corresponding silaboration products in moderate to excellent yields. In the
absence of an organic iodide, the silaboration gives products having completely
different regiochemistry. In the presence of an aldehyde, the silaboration
reaction afforded homoallylic alcohols in one pot in good to excellent yields,
with exceedingly high syn selectivity.
K.-J. Chang, D. K. Rayabarapu, F.-Y. Yang, C.-H. Cheng, J. Am. Chem. Soc.,
2005,127, 126-131.
Low catalyst loadings of (IPr)Pt(allyl ether) display enhanced activity and
regioselectivity for the hydrosilylation of terminal and internal alkynes.
Reactions lead to exquisite regioselectivity in favor of the cis-addition
product on the less hindered terminus of terminal and internal alkynes.
G. Berthon-Gelloz, J.-M. Schumers, G. De Bo, I. E. Markó, J. Org. Chem., 2008,
73, 4190-4197.
The use of a catalytic amount of PtCl2 enables the conversion of
α-hydroxypropargylsilanes to (Z)-silylenones through a highly selective
silicon migration via alkyne activation. The complementary (E)-silylenones are
accessed by a regioselective hydrosilylation of the ynone precursor.
D. A. Rooke, E. M. Ferreira, J. Am. Chem. Soc., 2010,
132, 11926-11928.
D. A. Rooke, E. M. Ferreira, J. Am. Chem. Soc., 2010,
132, 11926-11928.
The silicon nucleophile generated by copper(I)-catalyzed Si-B bond activation
allows several γ-selective propargylic substitutions. Chloride as a leaving
groups is superior in linear substrates, and the phosphate group produces superb
γ-selectivity in α-branched propargylic systems, and enantioenriched substrates
react with excellent central-to-axial chirality transfer.
D. J. Vyas, C. K. Hazra, M. Oestreich, Org. Lett., 2011,
13, 4462-4465.
A Rh-catalyzed coupling reaction between propargylic carbonates and a
silylboronate affords allenylsilanes in high yields. The reaction tolerates
various functional groups and proceeds with excellent chirality transfer.
H. Ohmiya, H. Ito, M. Sawamura, Org. Lett., 2009,
11, 5618-5620.
A copper-catalzed functionalization of propiolate esters with various Grignard
reagents in presence of trimethylsilyl trifluoromethanesulfonate enables the
synthesis of substituted E-vinyl silanes in good yields and excellent
diastereoselectivities via a catalytic carbocupration-silicon group migration
sequence.
A. J. Mueller Hendrix, M. P. Jennings, Org. Lett., 2010,
12, 2750-2753.
A new approach to 2-(arylmethyl)aldehydes begins
with a silylformylation reaction of terminal acetylenes with aryl- or
heteroarylsilanes, followed by treatment of the products with TBAF to induce a 1,2-anionotropic
rearrangement of the aryl group.
L. A. Aronica, P. Raffa, A. M. Caporusso, P. Salvadori, J. Org. Chem.,
2003, 5, 9292-9298.
Related
A new cyclopropenation reaction, which involves Cα-Si bond insertion of
alkylidene carbenes derived from α-silyl ketones, features excellent selectivity
for insertion into Cα-Si bonds rather than insertion into Cγ-H bonds or addition
to γ,δ-double or -triple bonds. The selectivity trend clearly indicates that the
α-oxygen in the tether significantly promotes Cγ-H insertion.
J. Li, C. Sun, D. Lee, J. Am. Chem. Soc., 2010,
132, 6640-6641.
