The synthesis of chlorosilanes from alkoxysilanes, silanols, and hydrosilanes with bulky substituents

Masaoka, Shin; Banno, Tadashi; Ishikawa, Mitsuo

doi:10.1016/j.jorganchem.2005.08.028

Cited by 24 publications

(13 citation statements)

References 33 publications

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“…CuCl 2 , which showed a high chlorination potency of CuCl 2 /CuI system . An almost quantitative (93–99%) tertiary hydrosilane chlorination by concentrated HCl under PdCl 2 catalysis was reported in 2006 . The same catalyst was utilized for the chlorination of polysiloxane bearing pendant Si‐H bonds by CCl 4 .…”

Section: Introductionmentioning

confidence: 99%

B(C₆F₅)₃ catalysis accelerates the hydrosilane chlorination by Ph₃CCl

Šimarek

Lamač

Horáček

et al. 2018

Applied Organom Chemis

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A chlorination of tertiary (5 examples), secondary (3 examples) and primary (PhSiH3) hydrosilanes by Ph3CCl with a catalytic amount of B(C6F5)3 is presented. The reaction was substantially faster than its non‐catalyzed version. The chlorination of secondary hydrosilanes and PhSiH3 proceeded in a stepwise manner, which allowed selective isolation of chlorohydrosilanes. The mechanism of catalytic hydrosilane chlorination seems to be distinct to mainstream B(C6F5)3 catalyzed reactions involving hydrosilanes (i.e. activation of Si‐H bond by the R3Si‐‐H‐‐B (C6F5)3 adduct formation). Contrary, the present process is based on an instant formation of [Ph3C]+[ClB(C6F5)3]− from B(C6F5)3 and Ph3CCl, followed by a hydride transfer from particular hydrosilane to tritylium cation with a concomitant generation of unstable silylium cation compensated by borate anion [ClB(C6F5)3]−. Subsequent decomposition of this ionic species leads to the corresponding chlorosilane and recuperation of B(C6F5)3.

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Section: Introductionmentioning

confidence: 99%

B(C₆F₅)₃ catalysis accelerates the hydrosilane chlorination by Ph₃CCl

Šimarek

Lamač

Horáček

et al. 2018

Applied Organom Chemis

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“…In the next step, we believe that the formed ethoxysilane is chlorinated in the presence of HCl to form the corresponding silyl chloride and EtOH. The chlorination of alkoxysilanes by HCl was previously reported by Ishikawa and co‐workers . We therefore believe that the active catalyst in this reaction is Et(H)O⋅B(C 6 F 5 ) 3 ( 3 ; Scheme ).…”

Section: Methodsmentioning

confidence: 52%

B(C₆F₅)₃‐Catalyzed Selective Chlorination of Hydrosilanes

Chulsky

Dobrovetsky

2017

Angewandte Chemie

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The chlorination of Si−H bonds often requires stoichiometric amounts of metal salts in conjunction with hazardous reagents, such as tin chlorides, Cl2, and CCl4. The catalytic chlorination of silanes often involves the use of expensive transition‐metal catalysts. By a new simple, selective, and highly efficient catalytic metal‐free method for the chlorination of Si−H bonds, mono‐, di‐, and trihydrosilanes were selectively chlorinated in the presence of a catalytic amount of B(C6F5)3 or Et2O⋅B(C6F5)3 and HCl with the release of H2 as a by‐product. The hydrides in di‐ and trihydrosilanes could be selectively chlorinated by HCl in a stepwise manner when Et2O⋅B(C6F5)3 was used as the catalyst. A mechanism is proposed for these catalytic chlorination reactions on the basis of competition experiments and density functional theory (DFT) calculations.

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“…70 The best method, though, is the simple treatment of TBSOH with concentrated aqueous HCl to provide the silyl chloride in 98% yield. 71 tert-Butyldimethylsilanol is also utilized to prepare more complex siloxysilanes. The title compound has been coupled with trimethylsilyl chloride, tert-butyldimethylsilyl chloride, and bis(dimethylsilyl)acetamide in the presence of an amine base to yield the disiloxanes.…”

Section: %mentioning

confidence: 99%

tert-Butyldimethylsilanol

Karabıyıkoğlu

Merlic

2014

Encyclopedia of Reagents for Organic Synthesis

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The synthesis of chlorosilanes from alkoxysilanes, silanols, and hydrosilanes with bulky substituents

Cited by 24 publications

References 33 publications

B(C₆F₅)₃ catalysis accelerates the hydrosilane chlorination by Ph₃CCl

B(C₆F₅)₃ catalysis accelerates the hydrosilane chlorination by Ph₃CCl

B(C₆F₅)₃‐Catalyzed Selective Chlorination of Hydrosilanes

tert-Butyldimethylsilanol

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The synthesis of chlorosilanes from alkoxysilanes, silanols, and hydrosilanes with bulky substituents

Cited by 24 publications

References 33 publications

B(C6F5)3 catalysis accelerates the hydrosilane chlorination by Ph3CCl

B(C6F5)3 catalysis accelerates the hydrosilane chlorination by Ph3CCl

B(C6F5)3‐Catalyzed Selective Chlorination of Hydrosilanes

tert-Butyldimethylsilanol

Contact Info

Product

Resources

About

B(C₆F₅)₃ catalysis accelerates the hydrosilane chlorination by Ph₃CCl

B(C₆F₅)₃ catalysis accelerates the hydrosilane chlorination by Ph₃CCl

B(C₆F₅)₃‐Catalyzed Selective Chlorination of Hydrosilanes