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.
Copper catalyzes a silylation of vinyliodonium salts with zinc-based silicon
reagents as nucleophiles to provide vinylsilanes in high yield likely via a Cu(I)/Cu(III)
reaction mechanism. The procedure is operationally simple, neither air- nor
moisture-sensitive, and tolerant of a range of functional groups.
L Zhang, M. Oestreich, Org. Lett.,
2018, 20, 8061-8063.
A bench-stable alkyl bisphosphine Mn(I) complex catalyzes an additive-free
Mn(I)-catalyzed dehydrogenative silylation of terminal alkenes. A broad variety
of aromatic and aliphatic alkenes was efficiently and selectively converted into
E-vinylsilanes and allylsilanes, respectively, at room temperature.
S. Weber, M. Glavic, B. Stöger, E. Pittenauer, M. Podewitz, L. F. Veiros, K.
Kirchner, J. Am. Chem. Soc.,
2021, 143, 17825-17832.
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.
Monothiolate-bridged dirhodium complexes can smoothly facilitate highly
regioselective and stereoselective hydrosilylation of terminal alkynes to afford
β(Z) vinylsilanes with good functional group compatibility.
X. Zhao, D. Yang, Y. Zhang, B. Wang, J. Qu, Org. Lett.,
2018, 20, 5357-5361.
Iron complexes bearing 2,9-diaryl-1,10-phenanthroline ligands exhibit not
only unprecedented catalytic activity but also unusual ligand-controlled
divergent regioselectivity in hydrosilylation reactions of various alkynes. This
highly efficient hydrosilylation provides useful di- and trisubstituted olefins
on a relatively large scale under mild conditions.
M.-Y. Hu, P. He, T.-Z. Qiao, W. Sun, W.-T. Li, J. Lian, J.-H. Li, S.-F. Zhu, J. Am. Chem. Soc.,
2020, 142, 16894-16902.
Iron complexes bearing 2,9-diaryl-1,10-phenanthroline ligands exhibit not
only unprecedented catalytic activity but also unusual ligand-controlled
divergent regioselectivity in hydrosilylation reactions of various alkynes. This
highly efficient hydrosilylation provides useful di- and trisubstituted olefins
on a relatively large scale under mild conditions.
M.-Y. Hu, P. He, T.-Z. Qiao, W. Sun, W.-T. Li, J. Lian, J.-H. Li, S.-F. Zhu, J. Am. Chem. Soc.,
2020, 142, 16894-16902.
A copper-catalyzed anti-Markovnikov hydrosilylation of alkynes with
PhSiH3 offers excellent recognition between terminal and internal
triple bonds. Various (hetero)aromatic and aliphatic substituted terminal
alkynes provides (E)-vinylsilanes in high yields and with excellent
regioselectivity.
Z.-Lu Wang, F.-L. Zhang, J.-L. Xu, C.-C. Shan, M. Zhao, Y.-H. Xu,
Org. Lett., 2020, 22, 7735-7742.
Manganese-photocatalyzed activation of the Si-H bond in silanes enables a mild
and efficient hydrosilylation of alkynes with high regioselectivity (anti-Markovnikov) and stereoselectivity
to provide a wide range of Z-vinylsilanes
in high yields. Moreover, visible-light-induced manganese-catalyzed activation
of the Ge-H bond enables an E-selective alkyne hydrogermylation.
H. Liang, Y.-X. Ji, R.-H. Wang, Z.-H. Zhang, B. Zhang,
Org. Lett., 2019, 21, 2750-2754.
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.
[Co(IAd)(PPh3)(CH2TMS)] exhibits high catalytic
efficiency and selectivity as well as good functional group compatibility in
alkyne hydrosilylation. Regio- and stereoselective hydrosilylations of
terminal, symmetrical internal, and trimethylsilyl-substituted unsymmetrical
internal alkynes provide β-(E)-silylalkenes, (E)-silylalkenes, and
(Z)-α,α-disilylalkenes, respectively, in high yields.
Z. Mo, J. Xiao, Y. Gao, L. Deng, J. Am. Chem. Soc.,
2014,
136, 17414-17417.
[RuHCl(CO)(H2IMes)(PCy3)] exhibits high catalytic
activity for the (Z)-selective hydrosilylation of various terminal
alkynes with 1,1,1,3,5,5,5-heptamethyltrisiloxane (HSiMe(OSiMe3)2).
Stereoretentive Hiyama coupling of the (Z)-alkenylsiloxanes allows the
synthesis of biologically active compounds.
Y. Mutoh, Y. Mohara, S. Saito, Org. Lett.,
2017, 19, 5204-5207.
The use of 1 mol % Eosin Y as a photocatalyst enables a visible light-promoted
hydrosilylation of alkynes in the presence of a catalytic amount of thiol as a
radical quencher to provide alkenylsilanes with high regio- and
stereoselectivites.
J. Zhu, W.-C. Cui, S. Wang, Z.-J. Yao, Org. Lett.,
2018, 20, 3174-3178.
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.
Very low loadings of a bench-stable cobalt(II) complex catalyze a
regioselective hydrosilylation of terminal alkynes. Both aromatic and aliphatic
alkynes could be effectively hydrosilylated with primary, secondary, and
tertiary silanes to give α-vinylsilanes in high yields with excellent
Markovnikov selectivity and extensive functional-group tolerance.
M. Skrodzki, V. Patroniak, P. Pawluć, Org. Lett., 2021, 23,
663-667.
A well-defined bidentate geometry-constrained iminopyridyl cobalt complex
enables an efficient and highly Markovnikov-selective hydrosilylation of
alkynes, featuring a broad substrate scope including aromatic/heteroaromatic/aliphatic
alkynes and primary/secondary silanes.
Z. Zong, Q. Yu, N. Sun, B. Hu, Z. Shen, X. Hu, L. Jin,
Org. Lett., 2019, 21, 5767-5772.
A bench-stable NNN pincer cobalt complex catalyzes a regioselective
hydrosilylation of terminal alkynes to provide a broad range of α-vinylsilanes in
good yields with up to 98/2 Markovnikov
regioselectivity. This very efficient protocol can be readily scaled up for gram-scale
synthesis.
S. Zhang, J. J. Ibrahim, Y. Yang, Org. Lett.,
2018, 20, 6265-6269.
A well-defined low-valent cobalt(I) catalyst [HCo(PMe3)4]
enables a highly regio- and stereoselective hydrosilylation of internal alkynes.
The reaction provides in many cases a single hydrosilylation isomer for various
hydrosilanes and unsymmetrical alkynes.
A. Rivera-Hernández, B. J. Fallon, S. Ventre, C. Simon, M.-H. Tremblay, G.
Gontard, E. Derat, M. Amatore, C. Aubert, M. Petit, Org. Lett.,
2016, 18, 4242-4245.
A highly regioselective, catalytic hydrosilylation of terminal allenes using
recyclable gold nanoparticles as catalyst does not require any external ligands
or additives. The hydrosilane addition takes place on the more substituted
double bond, which is attributed to steric and electronic factors.
M. Kidonakis, M. Stratakis, Org. Lett.,
2015,
17, 4538-4541.
A one-pot regioselective allene hydrosilylation/Pd(0)-catalyzed cross-coupling
protocol affords functionalized 1,1-disubstituted alkenes with excellent
regiocontrol. The regioselectivity of this hydroarylation is primarily governed
by N-heterocyclic carbene (NHC) ligand identity in the hydrosilylation
step and is preserved in the subsequent cross-coupling reaction.
Z. D. Miller, J. Montgomery, Org. Lett.,
2014,
16, 5486-5489.
In regioselective methods for allene hydrosilylation, alkenylsilanes are
produced via nickel catalysis with larger N-heterocyclic carbene (NHC)
ligands, whereas allylsilanes are produced via palladium catalysis with smaller
NHC ligands. These complementary methods allow either regioisomeric product to
be obtained with exceptional regiocontrol.
Z. D. Miller, W. Li, T. R. Belderrain, J. Montgomery, J. Am. Chem. Soc., 2013,
135, 15282-15285.
A silyl-Heck reaction allows the preparation of vinyl silyl ethers and
disiloxanes rom aryl-substituted alkenes and related substrates using a
commercially available catalyst system and mild conditions. This work represents
a highly practical means of accessing diverse classes of vinyl silyl ether
substrates in an efficient and direct manner with complete regiomeric and
geometric selectivity.
S. E. S. Martin, D. A. Watson, J. Am. Chem. Soc., 2013,
135, 13330-13333.
Palladium catalyzes a highly regio- and stereoselective hydrosilylation
applicable to a broad range of electron-deficient alkynes. The resulting
α-silylalkenes can be further transformated using particularly Hiyama coupling
and stereoinverting iododesilylation followed by Suzuki-Miyaura coupling, which
enables stereodivergent syntheses of α-arylenoates.
Y. Sumida, T. Kato, S. Yoshida, T. Hosoya, Org. Lett., 2012,
14, 1552-1555.
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 use of an iron precatalyst bearing an iminopyridine-oxazoline (IPO) ligand
enables a mild, regio- and stereoselective hydrosilylation of a broad range of
1,3-enynes with primary and secondary silanes to access 1,3-dienylsilanes. The
hydrosilylation proceeds via syn-addition of a Si-H bond to the alkyne group of
1,3-enynes, incorporating the silyl group at the site proximal to the alkene.
Z. Guo, H. Wen, G. Liu, Z. Huang, Org. Lett., 2021, 23,
2375-2379.
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.
Copper(I)-catalyzed propargylic substitution of linear precursors with one
equivalent of (Me2PhSi)2Zn predominantly yields the γ
isomer independent of the propargylic leaving group. The formed allenylic silane
can regioselectively react with a second equivalent of (Me2PhSi)2Zn
to give a bifunctional building block with allylic and vinylic silicon groups.
The propargylic displacement occurs quantitatively prior to the addition step.
C. K. Hazra, M. Oestreich, Org. Lett., 2012,
14, 4010-4013.
C. K. Hazra, M. Oestreich, Org. Lett., 2012,
14, 4010-4013.
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.
In the presence of Pd(0) and a phosphine, a hydrosilylation of 1,3-enynes
with Me2SiHCl yields dienylsilanes with (E)-configuration and
with the silicon group added to the internal alkyne carbon atom. Subsequent
hydrolysis gives silanols, that serve as precursors to conjugated dienes with
different substitution patterns.
H. Zhou, C. Moberg, Org. Lett., 2013,
15, 1444-1447.
Supported gold nanoparticles on metal oxides catalyze a cis-selective
disilylation of terminal alkynes with 1,2-disilanes in good isolated yields. The
reaction probably proceeds through oxidative insertion of the σ Si-Si bond on
gold followed by 1,2-addition to the alkyne.
C. Gryparis, M. Kidonakis, M. Stratakis, Org. Lett., 2013,
15, 6038-6041.
The presence of supported gold nanoparticles enables gold-catalyzed silaboration
of terminal alkynes with PhMe2SiBpin. The reaction proceeds at
ambient conditions in very good yields with a regioselectivity opposite to that
observed in the presence of Pd or Pt catalysts. The abnormal regioselectivity is
attributed to steric factors imposed by the Au nanoparticle during the
1,2-addition of silylborane to the alkyne.
C. Gryparis, M. Stratakis, Org. Lett., 2014,
16, 1430-1433.
Related
A C(sp3)-Si coupling of unactivated alkyl bromides with vinyl
chlorosilanes proceeds under mild conditions to provide alkylsilanes.
Functionalities such as Grignard-sensitive groups (e.g., acid, amide, alcohol,
ketone, and ester), acid-sensitive groups (e.g., ketal and THP protection),
alkyl fluoride and chloride, aryl bromide, alkyl tosylate and mesylate, silyl
ether, and amine were tolerated.
J. Duan, Y. Wang, L. Qi, P. Guo, X. Pang, X.-Z. Shu, Org. Lett., 2021, 23,
7855-7859.
An efficient Pd-catalyzed addition of boronic acids to silylacetylenes provides
β,β-disubstituted (E)- or (Z)-alkenylsilanes in good yields with
excellent regio- and stereoselectivity under mild reaction conditions. Moreover,
a sequential Pd-catalyzed boron addition/N-halosuccinimide-mediated
halodesilylation reaction results in a stereodivergent approach to
β,β-disubstituted alkenyl halides as versatile synthetic intermediates.
W. Kong, C. Che, J. Wu, L. Ma, G. Zhu, J. Org. Chem., 2014,
79, 5799-5805.
A facile synthesis of 1-silyl-substituted 1,3-butadienes is based on a [RuHCl(CO)(PCy3)2]-catalyzed
silylative coupling of terminal (E)-1,3-dienes with vinylsilanes. The
reaction provides (E,E)-dienylsilanes in a highly stereoselective fashion
with elimination of ethylene as a single byproduct.
J. Szudkowska-Frątczak, B. Marciniec, G. Hreczycho, M. Kubicki, P. Pawluć, Org. Lett.,
2015,
17, 2366-2369.
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.
Solvent-controlled hydroaluminations of Si-substituted alkynes with DIBAL-H
generate diastereomerically enriched alkenylaluminum reagents that
react with isocyanates at ambient temperature to afford
α-silyl-α,β-unsaturated amides in high yields. This method offers short reaction time, ease of purification, easily
accessible substrates, and gram-scale synthesis.
H. Lee, S. Cho, Y. Lee, B. Jung, J. Org. Chem., 2020, 85,
12024-12035.
