67473-43-2

Upstream product

• 3839-31-4 dimethyl(phenyl)silyl lithium 
• 623-70-1 ethyl (E)-crotonate 
• 10544-63-5 ethyl crotonate 
• 185990-03-8 dimethylphenyl(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)silane 
• 3839-31-4 dimethyl(phenyl)silyllithium 

Downstream Products

• 191916-72-0 (E)-5-(Dimethyl-phenyl-silanyl)-hex-2-enoic acid methyl ester 
• 191916-88-8 (Z)-5-(Dimethyl-phenyl-silanyl)-hex-2-enoic acid methyl ester 
• 191917-30-3 2-[3-(Dimethyl-phenyl-silanyl)-butylidene]-malonic acid dimethyl ester 

Relevant academic research and scientific papers

Synthesis of β-Silyl-α-amino Acid Derivatives by Cu-Catalyzed Regio- and Enantioselective Silylamination of α,β-Unsaturated Esters

A copper-catalyzed silylamination of α,β-unsaturated esters with silylboranes and hydroxylamines has been developed to afford the corresponding β-silyl-α-amino acid derivatives, which are of great interest in medicinal and pharmaceutical chemistry. Additionally, by using a suitable chiral bisphosphine ligand, the asymmetric induction is possible, delivering the optically active β-silyl-α-amino acids with synthetically acceptable diastereomeric ratios (55:45-82:18 dr) and high enantiomeric ratios (81:19-99:1 er).

Bench-Stable Stock Solutions of Silicon Grignard Reagents: Application to Iron- and Cobalt-Catalyzed Radical C(sp3)–Si Cross-Coupling Reactions

A robust method for the preparation of silicon-based magnesium reagents is reported. The MgBr2 used in the lithium-to-magnesium transmetalation step is generated in situ from 1,2-dibromoethane and elemental magnesium in hot THF. No precipitation of MgBr2 occurs in the heat, and transmetalation at elevated temperature leads to homogeneous stock solutions of the silicon Grignard reagents that are stable and storable in the fridge. This method avoids the preparation of silicon pronucleophiles such as Si?Si and Si?B reagents. The new Grignard reagents were applied to unprecedented iron- and cobalt-catalyzed cross-coupling reactions of unactivated alkyl bromides. The functional-group tolerance of these magnesium reagents is excellent.

Copper(II)-catalyzed silyl conjugate addition to α,β-unsaturated conjugated compounds: Bronsted base-assisted activation of Si-b bond in water

A mild method for the installation of the dimethylphenylsilyl group on the β-carbon of electron-deficient olefins is reported. In the presence of a catalytic amount of copper(II) (1 mol %) and amine base (5 mol %) at rt, the transformation proceeds effici

Conjugate additions of a simple monosilylcopper reagent with use of the CuI-DMS complex: Stereoselectivities and a dramatic impact by DMS

(Chemical Equation Presented) Conjugate additions utilizing the simple monosilylcuprate reagent Li[PhMe2SiCuI] to α,β-unsaturated carbonyl compounds are described. The presence of dimethyl sulfide (DMS), either as a component originating from t

Employing the simple monosilylcopper reagent, Li[PhMe2SiCuI], in 1,4-addition reactions

Conjugate addition reactions using the simple Li[PhMe2SiCuI] reagent to a variety of α,β-unsaturated carbonyl compounds is described; dimethyl sulfide from the purification of CuI plays a key role for very high yields as well as high stereosele

A synthesis of enantiomerically enriched propargyl silanes

Reduction of ethyl 3-methyl-, 3-isopropyl- and 3-n-pentyl-3-[dimethyl(phenyl)silyl]propanoates 4 with DIBAL to the aldehydes 5, enol trifluoromethanesulfonate (triflate) formation using trifluoromethanesulfonic (triflic) anhydride and 2,6-di-tert-butylpyridine, and elimination using LDA, gives the propargyl silanes 8. The esters 4 could also be prepared enantiomerically enriched (11), and the final products are the enantiomerically enriched propargyl (homochiral) silanes 14.

In search of open-chain 1,3-stereocontrol

Methylation of methyl 4-phenylpentanoate 25 gives the diastereoisomers methyl (2RS,4SR)-2-methyl-4-phenylpentanoate 26 and methyl (2RS,4RS)- 2-methyl-4-phenylpentanoate 27 in a ratio of 44:56. The aldehydes 3-dimethyl(phenyl)silylbutanal 28, 3-dimethyl(ph

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.