51425-55-9

Upstream product

• 14371-10-9 (E)-3-phenylpropenal 
• 75-77-4 chloro-trimethyl-silane 
• 105762-68-3 3-Phenyl-2-phenylsulfanyl-1-trimethylsilanyl-propan-1-ol 
• 108-86-1 bromobenzene 
• 107-02-8 acrolein 
• 104-53-0 3-phenyl-propionaldehyde 
• 109283-53-6 (E)-cinnamyloxytrimethylsilane 

Downstream Products

• 128586-68-5 2-allyl-3-phenylpropionaldehyde 
• 14371-10-9 (E)-3-phenylpropenal 
• 122-78-1 phenylacetaldehyde 
• 4432-63-7 2-phenylacrolein 

Relevant academic research and scientific papers

Stereoselective Synthesis of Trisubstituted Vinylboronates from Ketone Enolates Triggered by 1,3-Metalate Rearrangement of Lithium Enolates

An unprecedented stereoselective synthesis of trisubstituted vinylboronates is reported to proceed by direct borylation of lithium ketone enolates under transition-metal-free conditions. The stereospecific C?O borylation of lithium enolates was triggered by a carbonyl-induced 1,3-metalate rearrangement via a C-bound boron enolate. DFT calculations and control experiments revealed that the stereoselectivity is controlled by sterics. A variety of stereospecific trisubstituted vinylboronates, together with several tetrasubstituted vinylboronates, were conveniently synthesized with the newly developed methodology. Based on the transformation of stereospecific vinylboronate, a single isomer of Dienestrol was efficiently obtained.

Electrophilic trifluoromethylthiolation of carbonyl compounds

A general method for the α-trifluoromethylthiolation of carbonyl compounds, without prefunctionalization, has been developed. Aldehydes, ketones, esters, amides, keto-esters, alkaloids, and steroids have been trifluoromethylthiolated with good yields. This work, proposing a new reagent for electrophilic trifluoromethylthiolation, provides a route towards the original synthesis of various trifluoromethylthiolated molecules for further applications.

Mechanistic analysis of the photocycloaddition of silyl-tethered alkenes

(Chemical Equation Presented) The photochemistry of substituted cinnamyloxy silanes has been examined in both cyclohexane and acetonitrile solvents. Alkene isomerization occurs in addition to cycloaddition. Fluorescence quantum yields and excited singlet state lifetimes have been determined for each compound. We have used the information in order to better understand the regio- and stereoselectivity of photocycloaddition between silyl-tethered cinnamyl groups. This study allows us to conclude that the 2 + 2 photocycloaddition between alkenes is not a Woodward-Hoffmann orbital symmetry controlled event. The most consistent explanation for the excellent regio- and stereoselectivity is that the photocycloaddition is conformationally controlled.

Wittig rearrangement of lithiated allyl aryl ethers: A mechanistic study

At -75°C, α-lithiated allyl phenyl ether undergoes mainly the [1,2] Wittig rearrangement to afford, after acidic hydrolysis, 1-phenyl-2-propen-1-ol as the main product. A second metalation taking place at one of the ortho positions is the sole competing s

Facile synthesis of silyl enol ethers by Mg-promoted coupling of aliphatic carbonyl compounds with trimethylsilyl chloride

Treatment of aliphatic carbonyl compounds with trimethylsilyl chloride with Mg turning for Grignard reaction without any pre-treatment in N,N- dimethylformamide at room temperature brought about highly facile, effective and stereoselective coupling to give the corresponding silyl enol ethers in good yields.

CHLOROSILANE-ACCELERATED CONJUGATE ADDITION OF CATALYTIC AND STOICHIOMETRIC ORGANOCOPPER REAGENTS

Trialkylsilyl chlorides, particularly in combination with hexamethylphosphoramide or 4-dimethylaminopyridine, dramatically accelerates the conjugate addition of catalytic and stoichiometric organocopper reagents onto enones, enals, and enoates, in which very high degrees of stereo- and chemoselectivities were observed.

Silyl Ketone Chemistry. Synthesis of Regio- and Stereoisomerically Pure Enol Silyl Ethers Using α-Phenylthio Silyl Ketones

The addition of a number of organometallic reagents to α-phenylthio silyl ketones proceeds with good to excellent diastereoselectivity.The products undergo Brook rearrangement and fragmentation to enol silyl ethers with, in most cases, excellent stereoche

Me3SiCl/HMPA ACCELERATED CONJUGATE ADDITION OF CATALYTIC COPPER REAGENT. STEREOSELECTIVE SYNTHESIS OF ENOL SILYL ETHER OF ALDEHYDE

Copper-catalyzed conjugate addition of Grignard reagents in the presence of Me3SiCl and HMPA proceeds in much higher yield than the reaction of conventional organocopper reagents and shows very good regio-, stereo-, and chemoselectivities.

REACTIVITE DES DERIVES ORGANOCUIVREUX VIS-A-VIS DES ALDEHYDES αβ-ETHYLENIQUES

Secondary lithium dialkylcuprates react with αβ-ethylenic aldehydes to give a mixture of 1,2 and 1,4 addition products.Only 1,2 addition products are obtained with allylic and acetylenic cuprates whereas homallylic, phenyl and vinylic cuprates give 1,4 addition products.The 1,4/1,2 ratio also depends on the nature of the metal in the cuprate (Mg or Li).Thus chloromagnesium dimethyl cuprate, in THF, is the most favorable compound to give the 1,4 addition product.