Categories: C-Si Bond Formation > Silanes
Synthesis of allylsilanes
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A palladium-catalyzed allylic silylation using allylic alcohols and disilanes as
precursors proceeds smoothly under mild and neutral conditions and is suitable
for synthesis of regio- and stereodefined allylsilanes. The presented silylation
reaction can be easily extended to include synthesis of allylboronates by change
of the dimetallic reagent.
N. Selander, J. R. Paasch, K. J. Szabó, J. Am. Chem. Soc., 2011,
133, 17701-17703.
A second-generation ligand, bis(3,5-di-tert-butylphenyl)(tert-butyl)phosphine,
enables the preparation of allylsilanes using the palladium-catalyzed silyl-Heck
reaction. This ligand provides nearly complete suppression of starting material
alkene isomerization.
J. R. McAtee, G. P. A. Yap, D. A. Watson, J. Am. Chem. Soc., 2014,
136, 10166-10172.
Modulating the steric and electronic properties of the ligands on a
nickel catalyst enables a Ni/Cu-catalyzed regiodivergent synthesis of
allylsilanes directly from allylic alcohols. Good yields and excellent
selectivity were obtained with linear and α-branched allylic alcohols as
substrates.
Y. Gan, W. Xu, Y. Liu,
Org. Lett., 2019, 21, 9652-9657.
Modulating the steric and electronic properties of the ligands on a nickel
catalyst enables a Ni/Cu-catalyzed regiodivergent synthesis of allylsilanes
directly from allylic alcohols. Good yields and excellent selectivity were
obtained with linear and α-branched allylic alcohols as substrates.
Y. Gan, W. Xu, Y. Liu,
Org. Lett., 2019, 21, 9652-9657.
A NiCl2(PMe3)2-catalyzed reaction of allyl alcohols with silylzinc reagents,
including PhMe2SiZnCl, Ph2MeSiZnCl, and Ph3SiZnCl,
provides
allylsilanes in high yields. The reaction
exhibited high regioselectivity and E/Z-selectivity when 1- or
3-aryl-substituted allyl alcohols were used as the substrates.
B. Yang, Z.-X. Wang,
Org. Lett., 2019, 21, 7965-7969.
Copper-catalyzed regiodivergent hydrosilylation reactions of substituted
1,3-dienes with hydrosilanes provide 1,2- and 1,4-hydrosilylated products
depending on the catalytic systems. A 1,4-hydrosilylation reaction of
2-aryl-substituted 1,3-dienes with diphenylsilane was also successfully realized.
These methods provide convenient and efficient approaches to structurally
diverse allylsilanes.
Z.-L. Wang, Y. Wang, J.-L. Xu, M. Zhao, K.-Y. Dai, C.-C. Shan, Y.-H. Xu, Org. Lett., 2021, 23,
4736-4742.
Copper-catalyzed regiodivergent hydrosilylation reactions of substituted
1,3-dienes with hydrosilanes provide 1,2- and 1,4-hydrosilylated products
depending on the catalytic systems. A 1,4-hydrosilylation reaction of
2-aryl-substituted 1,3-dienes with diphenylsilane was also successfully realized.
These methods provide convenient and efficient approaches to structurally
diverse allylsilanes.
Z.-L. Wang, Y. Wang, J.-L. Xu, M. Zhao, K.-Y. Dai, C.-C. Shan, Y.-H. Xu, Org. Lett., 2021, 23,
4736-4742.
The use of a bisphosphine ligand with a rigid backbone enables a
copper-catalyzed regioselective Markovnikov 3,4-hydrosilylation of 2-substituted
1,3-dienes in better yield and selectivity.
Y. Wang, Z.-L. Wang, W.-W. Ma, Y.-H. Xu, Org. Lett.,
2022, 24, 4081-4086.
An open-bent titanocene complex [Me2C(C5H4)2TiMe2]
proved to be efficient for the hydrosilylation of a variety of substrates such
as disubstituted dienes, activated alkenes, and even an alkyne.
R. Pop, J. L. Cui, L. Adriaenssens, V. Comte, P. Le Gendre, Synlett, 2011,
679-683.
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.
Pd-catalyzed silylation of allylic phenyl ethers as electrophiles with
organodisilanes can be run at room temperature in water as the only medium using
micellar catalysis.
R. Moser, T. Nishikata, B. H. Lipshutz, Org. Lett., 2010,
12, 28-31.
A copper-catalyzed regiodivergent hydrosilylation of a wide range of simple
allenes provides linear and branched allylsilanes depending on the choice of
solvents. Furthermore, branched allylsilanes were obtained with high
enantioselectivity in the presence of a C2-symmetric bisphosphine ligand.
J.-L. Xu, Z.-Y. Xu, Z.-L. Wang, W.-W. Ma, X.-Y. Sun, Y. Fu, Y.-H. Xu, J. Am. Chem. Soc.,
2022, 144, 5535-5542.
A copper-catalyzed regiodivergent hydrosilylation of a wide range of simple
allenes provides linear and branched allylsilanes depending on the choice of
solvents. Furthermore, branched allylsilanes were obtained with high
enantioselectivity in the presence of a C2-symmetric bisphosphine ligand.
J.-L. Xu, Z.-Y. Xu, Z.-L. Wang, W.-W. Ma, X.-Y. Sun, Y. Fu, Y.-H. Xu, J. Am. Chem. Soc.,
2022, 144, 5535-5542.
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 new method for the synthesis of substituted 2-acylallylmetal reagents in a
highly regio- and stereoselective fashion involving a three-component assembly
of allenes, acyl chlorides, and bimetallic reagents (B-B, Si-Si, and Sn-Sn)
catalyzed by phosphine-free palladium complexes is described.
F.-Y. Yang, M. Shanmugasundaram, S.-Y. Chuang, P.-J. Ku, M.-Y. Wu, C.-H. Cheng,
J. Am. Chem. Soc.,
2003, 125, 12576-12583.
An enantioselective silaboration of allenes was achieved using an achiral
silylborane in the presence of a palladium catalyst bearing a chiral
monodentate phosphine ligand. The enantioselectivity depended on the
bulkiness of substituents of allenes.
T. Ohmura, H. Taniguchi, M. Suginome, J. Am. Chem. Soc., 2006, 128, 13682-13683.
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.
