18042-35-8

Upstream product

• 766-77-8 Dimethylphenylsilane 
• 78-94-4 methyl vinyl ketone 
• 1833-51-8 chloromethyldimethylphenylsilane 
• 17932-70-6 [(dimethyl-phenyl-silanyl)-methyl]-malonic acid diethyl ester 
• 18192-31-9 ethyl 3-(dimethylphenylsilyl)propionate 
• 17872-96-7 3-[(dimethyl)phenylsilyl]propionic acid 
• 769-00-6 (iodomethyl)dimethylphenylsilane 
• 1145-98-8 1,2-diphenyltetramethyldisilane 
• 768-33-2 phenyldimethylsilyl chloride 
• 3839-31-4 dimethyl(phenyl)silyllithium 
• 57519-88-7 1,1-dichloro-1-phenyl-2,2,2-trimethyldisilane 
• 17983-34-5 3-(dimethyl(phenyl)silyl)propionyl chloride 
• 506-82-1 dimethylcadmium 

Downstream Products

• 18410-34-9 3-(dimethylphenylsilyl)-1,1-dimethyl-1-propanol 
• 109023-17-8 [Dimethyl-(3-trimethylsilanyloxy-but-3-enyl)-silanyl]-benzene 

Relevant academic research and scientific papers

Visible-Light-Mediated Metal-Free Hydrosilylation of Alkenes through Selective Hydrogen Atom Transfer for Si?H Activation

Although there has been significant progress in the development of transition-metal-catalyzed hydrosilylations of alkenes over the past several decades, metal-free hydrosilylation is still rare and highly desirable. Herein, we report a convenient visible-

1,3-γ-Silyl-elimination in electron-deficient cationic systems

Placement of an electron-withdrawing trifluoromethyl group (-CF 3) at a putative cationic centre enhances γ-silyl neighbouring-group participation (NGP). In stark contrast to previously studied γ-silyl-substituted systems, the preferred reaction pathway is 1,3-γ-silyl elimination, giving ring closure over solvent substitution or alkene formation. The scope of this cyclopropanation reaction is explored for numerous cyclic and acyclic examples, proving this method to be a viable approach to preparing CF3-substituted cyclopropanes and bicyclic systems, both containing quaternary centres. Rate-constants, kinetic isotope effects, and quantum mechanical calculations provided evidence for this enhancement and further elaborated the disparity in the reaction outcome between these systems and previously studied γ-silyl systems.

Palladium/Me3SiOTf-catalyzed bis-silylation of α,β-unsaturated carbonyl compounds without involving oxidative addition of disilane

In the presence of a catalytic amount of Me3SiOTf and palladium(0), the addition of disilane to α,β-unsaturated carbonyl compounds proceeds under very mild conditions via η3-siloxyallylpalladium generated by the reaction of enone, en

A synthesis of (±)-lavandulol using a silyl-to-hydroxy conversion in the presence of 1,1-disubstituted and trisubstituted double bonds

Silylcuprates and silylzincates react with α,β-unsaturated aldehydes, esters, ketones and amides 19 unsubstituted at the β-position in higher yield if trimethylsilyl chloride is present. Applying this method, conjugate addition of the silylcuprate 26 derived from (Z)-chloro(2-methylbut-2-enyl)diphenylsilane 24, itself prepared by an improved route, to 3-methylene-6-methylhept-5-en-2-one 25 gave 3-[(Z)-2-methylbut-2-enyl(diphenyl)silyl]methyl-6-methylhept-5-en-2-one 27. A Wittig reaction gave 3-[(Z)-2-methylbut-2-enyl(diphenyl)silyl]methyl-2,6-dimethylhepta-1,5-diene 28 and silyl-to-hydroxy conversion gave lavandulol 1, even in the presence of the 1,1-disubstituted and trisubstituted double bonds. The hydroxy group of the 3-hydroxysilane, 2,6-dimethyl-3-{[(Z)-2-methylbut-2-enyl]diphenylsilyl}methylhept-5-en-2-ol 30, activated the allylsilane group towards protodesilylation. Chloro(diphenyl)methallylsilane 35 is easier to make than the chloride 24, and should be an alternative allylsilane that can make a lithium and hence a cuprate reagent like 26.

Conjugate addition of silyl groups to β-unsubstituted enones, and Si-to-OH conversion: A synthesis of (±)-lavandulol

TMS chloride raises the yield in the conjugate addition of silylcuprates and zincates to β-unsubstituted enones, and Si-to-OH conversion is possible using the 2-methylbut-2-enyl(diphenyl)silyl group in the presence of highly nucleophilic alkenes. Both reactions are used in a synthesis of lavandulol.

Catalytic asymmetric synthesis of β-hydroxy ketones by palladium-catalyzed asymmetric 1,4-disilylation of α,β-unsaturated ketones

1,4-Disilylation of β,β-unsaturated ketones with 1,1-dichloro-1-phenyl-2,2,2-trimethyldisilane proceeded in the presence of phosphine-palladium catalysts in benzene. High enantio-selectivity (up to 92%) was observed in the disilylation with dichloro[(R)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl] palladium(II) as a catalyst (0.5 mol %). The disilylation products, 1-(trimethyisilyloxy)-3-(dichlorophenylsilyl)propenes, were readily converted into optically active α-unsubstituted or anti α-substituted β-(phenyldimethylsilyl) ketones, the oxidation of which gave the corresponding optically active β-hydroxy ketones in high yields.

1,4-Addition of Triorganozincates and Silyldiorganozincates to α,β-Unsaturated Ketones

Lithium and magnesium triorganozincates, prepared by combination of ZnCl2(TMEDA) with 3 molar equivalents of RLi or RMgX, or from dialkylzinc and 1 molar equivalent of RLi or RMgX, react with 2-cyclohexen-1-one (1) under mild conditions to produce moderate to good yields of the 1,4-addition products 2.The approximate reactivity order obtained from the product distribution using unsymmetrical zincates is tBuCH2 tBu, Me Me2PhSi.The latter groups are transferred with good selectivity from mixed reagents derived from Me2Zn.This sequence differs strikingly from that exhibited by unsymmetrical cuprates which transfer neopentyl very easily, and also tert-butyl more easily than the corresponding zincates.The methylation with Me3ZnLi is catalyzed by cobalt complexes.Other enones (7-13) generally give poor yields, and the cobalt-catalyzed methylation of isophorone (3) is complicated by a Kharasch-type deconjugation.Mixed silyldialkylzincates, Me2PhSiZnR2Li, produce the β-silyl ketones from a variety of unhindered or moderately hindered enones in practically useful yields; one example of an α,β-unsaturated ester (12) is also included.

The Conjugate Addition of a Silyl Group to Enones and its Removal with Copper(II) Bromide: A Protecting Group for the αβ-Unsaturation of αβ-Unsaturated Ketones

Silyl-lithium reagents mixed with copper(I) salts react with enones, including esters and aldehydes, to give β-silyl carbonyl compounds in good yield.The β-silylketones can be used in synthesis without risk to the silyl group and the enone group can be restored by bromination-desilylbromination with copper(II) bromide.The principle is illustrated with syntheses of carvone and dihydrojasmone.