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.

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.

Gold nanoparticles supported on ZrO₂ efficiently generate alkyl radicals via homolysis of unactivated C(sp³)-O bonds. A subsequent C(sp³)-Si bond formation provides diverse organosilicon compounds. A wide array of esters and ethers participated in the heterogeneous gold-catalyzed silylation by disilanes to give diverse alkyl-, allyl-, benzyl-, and allenyl silanes in high yields.
H. Miura, M. Doi, Y. Yasui, Y. Masaki, H. Nishio, T. Shishido, J. Am. Chem. Soc., 2023, 145, 4613-4625.

Phosphonium salts catalyze a coupling of both activated and nonactivated alkyl halides with both trichlorosilane and methyldichlorosilane. A wide variety of silyl-functionalized compounds may be prepared easily and in good yields.
Y. S. Cho, S.-H. Kang, J. S. Han, B. R. Yoo, I. N. Jung, J. Am. Chem. Soc., 2001, 123, 5584-5585.

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.

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.

Commercially available lithium triethylborohydride (LiHBEt₃) catalyzes a transition-metal-free hydrosilylation of allenes to provide (E)-allylsilanes in good yields. Both mono- and disubstituted allenes could be hydrosilylated with primary or secondary silanes effectively.
Z.-K. Liu, B. Wang, Y. Liu, Z.-Q. Zhang, Z.-P. Zhang, J. Org. Chem., 2023, 88, 12257-12264.

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.