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Synthesis of alkylsilanes


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Organofluorophosphonium salts exhibit Lewis acidity derived from a low-lying σ* orbital at P opposite F. Due to the acidity, these salts for example catalyze the rapid isomerization of 1-hexene to 2-hexene and a cationic polymerization of isobutylene. In the presence of hydrosilanes and a catalytic amount of an organofluorophosphonium salt, olefins and alkynes undergo efficient hydrosilylation.
M. Pérez, L. J. Hounjet, C. B. Caputo, R. Dobrovetsky, D. W. Stephan, J. Am. Chem. Soc., 2013, 135, 18308-18310.

Using triethylborane as the initiator, phenyldimethylsilane and trichlorosilane undergo efficient radical hydrosilylation reactions with various alkenes. Adducts from the trichlorosilane reactions can be oxidised to afford alcohols in moderate yields. This two-step process leads to the anti-Markovnikov hydration of alkenes.
M. J. Palframan, A. F. Parsons, P. Johnson, Synlett, 2011, 2811-2814.

The combination of NiCl2·6H2O/tBuOK catalyzes an electrophilically activated hydrosilylation of terminal alkenes with primary silanes under mild reaction conditions with excellent performance, exclusive anti-Markovnikov selectivity, broad functional group tolerance, and good scalability. However, secondary and tertiary silanes are not suitable.
X. Wu, G. Ding, W. Lu, L. Yang, J. Wang, Y. Zhang, X. Xie, Z. Zhang, Org. Lett., 2021, 23, 1434-1439.

Gaseous and flammable silanes are inconvenient to use in chemical reactions. Catalytic amounts of a nickel pincer complex and NaOtBu enable the synthesis of alkyl hydrosilanes from alkenes and alkoxy hydrosilanes. The scope and mechanism of the hydrosilylation reactions are also described.
I. Buslov, S. C. Keller, X. Hu, Org. Lett., 2016, 18, 1928-1931.

An iron-catalyzed highly Markovnikov-type selective and enantioselective hydrosilylation of terminal aliphatic alkenes with good functional group tolerance provides valuable chiral organosilanes with high ees. Chiral aliphatic alkan-2-ols could be efficiently synthesized via further derivatization of chiral organosilanes without any racemization.
B. Cheng, W. Liu, Z. Lu, J. Am. Chem. Soc., 2018, 140, 5014-5017.

Pincer iron complexes with electron-donating phosphinite-iminopyridine (PNN) ligands are efficient catalysts for the anti-Markovnikov alkene hydrosilylation of primary, secondary, and tertiary silanes. More importantly, the system tolerates reactive groups such as ketones, esters, and amides. Furthermore, the iron catalysts may provide a low-cost and environmentally benign alternative to currently employed systems for alkene hydrosilylation.
D. Peng, Y. Zhang, X. Du, L. Zhang, X. Leng, M. D. Walter, Z. Huang, J. Am. Chem. Soc., 2013, 135, 19154-19166.

A Co catalyst for anti-Markovnikov alkene hydrosilylation can be generated in situ from an air-stable precursor that is simple to synthesize from low-cost, commercially available materials. This inexpensive catalyst can be used without added solvent at low temperatures with low loadings. In addition, a mixture of Co catalysts performs a tandem catalytic alkene isomerization/hydrosilylation reaction.
C. Chen, M. B. Hecht, A. Kavara, W. W. Brennessel, B. Q. Mercado, D. J. Weix, P. L. Holland, J. Am. Chem. Soc., 2015, 137, 13244-13247.

Photocatalytic in situ generations of both secondary and tertiary silyl radicals by one-electron oxidation of ate complexes, formed from silylboranes and an alkoxide cocatalyst, achieve highly efficient hydrosilylation and deuterosilylation of electron-rich alkenes and dienes as well as electron-deficient alkenes.
R. Arai, Y. Nagashima, T. Koshikawa, K. Tanaka, J. Org. Chem., 2023, 88, 10371-10380.

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.

The reaction of unactivated secondary and primary alkyl chlorides as well as primary alkyl triflates with silyl lithium reagents provides tetraorganosilanes in good yields in the absence of any transition metal catalyst under mild conditions. The silyl lithium reagents are readily generated from the corresponding commercially available chlorosilanes.
S. Mallick, E.-U. Würthwein, A. Studer, Org. Lett., 2020, 22, 6568-6572.

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.

Palladium-Catalyzed Cross-Coupling of Silyl Electrophiles with Alkylzinc Halides: A Silyl-Negishi Reaction
A. P. Cinderella, B. Vulovic, D. A. Watson, J. Am. Chem. Soc., 2017, 139, 7741-7744.

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.

In a nucleophilic displacement of the triflate leaving group attached to terminally functionalized alkyl groups, copper catalysis is used to release the silicon nucleophile from Suginome's Si-B reagent. The functional group tolerance is excellent, the reaction even tolerates halide leaving groups.
J. Scharfbier, M. Oestreich, Synlett, 2016, 27, 1274-1276.

A simple, commercially available nickel catalyst (NiBr2·diglyme) can achieve couplings of unactivated alkyl bromides with nucleophilic silicon reagents under unusually mild conditions.
C. K. Chu, Y. Liang, G. C. Fu, J. Am. Chem. Soc., 2016, 138, 6404-6407.

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.

A cobalt-catalyzed enantioselective hydrosilylation of terminal alkenes enables an efficient synthesis of valuable chiral dihydrosilanes. This protocol is operationally simple and atom-economic using relatively simple and readily available starting materials.
B. Cheng, P. Lu, H. Zhang, X. Cheng, Z. Lu, J. Am. Chem. Soc., 2017, 139, 9439-9442.

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.

Allylsilylation allows to install both silyl and allyl groups onto a carbon-carbon double bond directly. Proton-exchanged montmorillonite showed excellent catalytic performances for the allylsilylation of alkenes. Isolation of the reaction intermediate on the montmorillonite surface helped to investigate the reaction mechanism.
K. Motokura, S. Matsunaga, A. Miyaji, Y. Sakamoto, T. Baba, Org. Lett., 2010, 12, 1508-1511.

Electroreduction of readily available chlorosilanes enables a new strategy for silyl radical generation via energetically uphill reductive cleavage of strong Si-Cl bonds at highly biased potentials. This convenient and transition-metal-free strategy proved to be general in various alkene silylation reactions including disilylation, hydrosilylation, and allylic silylation.
L. Lu, J. C. Siu, Y. Lai, S. Lin, J. Am. Chem. Soc., 2020, 142, 20979-20986.

A water-insoluble copper(II) acetylacetonate-chiral bipyridine complex catalyzed an asymmetric silyl conjugate addition of lipophilic substrates in water. Indeed, the reactions proceeded efficiently only in water. Water seems to play a role in constructing and stabilizing sterically confined transition states and accelerating subsequent protonation.
T. Kitanosono, L. Zhu, C. Liu, P. Xu, S. Kobayashi, J. Am. Chem. Soc., 2015, 137, 15422-15425.

Irradiating 3-silyl-1,4-cyclohexadienes with blue light in the presence of a commercially available photocatalyst smoothly generated silyl radicals bearing various substituents. A subsequent trapping by a broad range of alkenes affords products in good yields within 1 h. This photoredox-induced homolysis enables also an efficient generation of germyl radicals.
B.-X. Li, H. Ishida, C. Wang, M. Uchiyama, Org. Lett., 2023, 25, 1765-1770.

The use of Martin's spirosilane-derived pentacoordinate silylsilicates as silyl radical precursors enables a visible-light-induced hydrosilylation of a broad range of alkenes and alkynes, as well as the C-H silylation of heteroarenes. Remarkably, Martin’s spirosilanes were stable and could be recovered via a simple workup process.
Y. Zhao, Y. Wan, Q. Yuan, J. Wei, Y. Zhang, Org. Lett., 2023, 25, 1386-1391.

The presence of a catalytic amount of copper(II) and an amine base enables a mild method for the installation of the dimethylphenylsilyl group on the β-carbon of electron-deficient olefins at rt. The transformation proceeds efficiently in water within 1.5–5 h to afford β-silylated products in good yields.
J. A. Calderone, W. L. Santos, Org. Lett., 2012, 14, 2090-2093.

A rhodium-catalyzed enantioselective hydrosilylation of unactivated internal alkenes bearing a polar amide group for coordination assistance provides silanes with high regio- and enantioselectivity.
W-R. Zhang, W.-W. Zhang, H. Li, B.-J. Li, Org. Lett., 2023, 25, 1667-1672.

Supported Au nanoparticles on TiO2 catalyze the insertion of carbenes from α-diazocabonyl compounds into hydrosilanes without ligands or additives. This purely heterogeneous process allows the recycling and reuse of the catalyst.
M. Kidonakis, M. Stratakis, Org. Lett., 2018, 20, 4086-4089.

A chiral spiro-bisoxazoline ligand has proven to be an optimal ligand for an asymmetric iron-catalyzed enantioselective Si-H bond insertion reaction of α-diazoesters to provide chiral α-silyl esters in good yields with high enantioselectivities. The reaction proceeds via a concerted quintet transition state.
H. Gu, Z. Han, H. Xie, X. Lin, Org. Lett., 2018, 20, 6544-6549.

An efficient copper-catalyzed carbenoid insertion reaction of α-diazo carbonyl compounds into Si-H and S-H bonds provides a broad range of α-silylesters and α-thioesters in high yields using 5 mol% of a simple copper(I) salt as catalyst. In addition, α-diazoketones can be converted to α-silylketones in moderate yields.
H. Keipour, A. Jalba, L. Delage-Laurin, T. Ollevier, J. Org. Chem., 2017, 82, 3000-3010.

An efficient carbene insertion reaction of α-diazoesters into Si-H bond provides a wide range of α-silylesters in high yields using a simple iron(II) salt as catalyst.
H. Keipour, T. Ollevier, Org. Lett., 2017, 19, 5736-5739.

In the presence of cationic rhodium complexes, Si-B compounds function as equivalents of nucleophilic silicon, which is efficiently transferred onto acyclic as well as cyclic α,β-unsaturated carbonyl compounds. [((S)-binap)Rh(cod)]ClO4 has effected an asymmetric 1,4-addition to cyclic acceptors in high enantiomeric excess.
C. Walter, G. Auer, M. Oestreich, Angew. Chem. Int. Ed., 2006, 45, 5675-5677.

A convenient method for the synthesis of 1,1-diboronates from the corresponding N-tosylhydrazones is also applicable to 1-silyl-1-boron compounds. Derivatization and consecutive Pd-catalyzed cross-coupling reactions with 1,1-boronates were also explored, demonstrating the synthetic potential of 1,1-diboronates.
H. Li, X. Shangguan, Z. Zhang, S. Huang, Y. Zhang, J. Wang, Org. Lett., 2014, 16, 448-451.

A platinum-catalyzed intramolecular silaboration of borylsilanyl homoallyl ethers gave 1-oxa-2-silacyclopentanes in high yields. The stereoselectivity of the reactions strongly depended on the used ligands. A complementary synthesis of a pair of diastereomers of 6-methylheptane-1,3,5-triol is described.
T. Ohmura, H. Furukawa, M. Suginome, J. Am. Chem. Soc., 2006, 128, 13366-13367.

T. Ohmura, H. Furukawa, M. Suginome, J. Am. Chem. Soc., 2006, 128, 13366-13367.

Highly efficient, stereo- and regioselective palladium-catalyzed hydro-, sila-, and stannastannations of cyclopropenes gave multisubstituted cyclopropylstannanes. The addition across the double bond proceeds from the least hindered face.
M. Rubina, M. Rubin, V. Gevorgyan, J. Am. Chem. Soc., 2002, 124, 11566-11567.


A Ni-H-catalyzed hydroalkylation of vinylsilanes and -germanes as well as allylsilanes with unactivated alkyl iodides proceeds with anti-Markovnikov selectivity to deliver the linear regioisomer. Mechanistic control experiments support a radical mechanism, and a competition experiment reveals that the chemoselectivity is in favor of the vinyl over the allyl group.
D. Brösamlen, M. Oestreich, Org. Lett., 2023, 25, 5319-5323.