69358-34-5

Upstream product

• 4187-87-5 1-Phenyl-2-propyn-1-ol 
• 108-98-5 thiophenol 
• 100-68-5 methyl-phenyl-thioether 
• 699-12-7 2-(phenylthio)ethanol 
• 100-52-7 benzaldehyde 
• 1822-73-7 phenylthioethylene 
• 62762-20-3 1-phenylthio-1-trimethylsilylethene 
• 77298-24-9 2-methoxyethyl phenyl sulfide 

Downstream Products

• 107978-06-3 (R)-1-phenyl-2-(phenylthio)propan-1-one 

Relevant academic research and scientific papers

High-Atom Economic Approach to Prepare Chiral α-Sulfenylated Ketones

Chiral α-sulfenylated ketones are versatile building blocks, although there are still several limitations with their preparation. Here we report a new two-step procedure, consisting of Pd-catalyzed hydrothiolation of propargylic alcohols followed by an enantioselective Rh isomerization of allylic alcohols. The isomerization reaction is the key step for obtaining the ketones in their enantioenriched form. The new methodology has a high atom economy and induces good to high levels of enantioselectivity; no waste is produced. A mechanism involving a Rh-hydride-enone intermediate is proposed for the isomerization reaction.

Polylithiation of thioethers: A versatile route for polyanionic synthons

The successive reaction of phenyl vinyl thioether (1) with n-butyllithium and an electophile [E1=PhCHO, (CH2)4CO, (CH2)5CO] in THF at - 78°C gives, after hydrolysis, the expected methylenic hydroxy thioethers (2). Deprotonation of 2 with n-butyllithium followed by a DTBB-catalysed lithiation and reaction with a second electrophile [E2=tBuCHO, PhCHO, Me2CO, (CH2)5CO], at - 78°C, gives after hydrolysis the corresponding methylenic diols 3. The same diols can be prepared starting from 1 in a one-pot process without isolation of the hydroxy thioether 2. The same methodology was applied to the cyclopropyl phenyl thioether (4), cyclopropyl 1,3-diols 5 {E1=tBuCHO, PhCHO, [Me(CH2)4]2CO, (CH2)5CO, (CH2)7CO; E2=tBuCHO, Me2CO, (CH2)5CO} being isolated in moderate yields. The successive treatment of bis(phenylthio)methane (7) with: (a) n-butyllithium at 0°C, (b) a carbonyl compound [E1=tBuCHO, Me2CO, Et2CO, (CH2)5CO] at - 40°C, (c) lithium and catalytic amount of DTBB (5%) and (d) a second carbonyl compound [E2=iPrCHO, tBuCHO, Me2CO, Et2CO, (CH2)5CO] both at - 78°C leads, after hydrolysis, to the expected dihydroxy thioethers 8. When after step (d), a second DTBB-catalysed lithiation is performed at temperatures ranging between - 78 and 20°C, the corresponding allylic alcohols 9 were isolated. Finally, treatment of alcohols 9 with a few drops of 6 M hydrochloric acid gives dienes 10 in almost quantitative yields.

Phenyl vinyl thioether: A convenient source of the ethylene 1,1-dianion

The successive reaction of phenyl vinyl thioether (1) with n-butyllithium and an electrophile [E1= PhCHO, (CH2)4CO, (CH2)5CO] in THF at -78°C gives, after hydrolysis, the expected methylenic hydroxy t

CLEAVAGE OF SILICON-VINYL CARBON BOND BY nBu4NF

Dimethylphenylsilyl- and diphenylmethylsilyl-vinyl carbon bonds are cleaved with nBu4NF.Desilylation of 1-phenylthio-1-trimethylsilyl-1-alkenes in the presence of aldehyde moiety gives carbanion adducts.

A CONVENIENT MATHOD FOR PREPARATION OF 1-(METHYLTHIO) AND 1-(PHENYLTHIO)VINYLLITHIUM REAGENTS

1-(Methylthio) and 1-(phenylthio)vinyllithiums were prepared by the treatment of the corresponding 2-methoxyethyl sulfides with twice molar amounts of butyllithium in the presence of N,N,N',N'-tetramethylethylenediamine (TMEDA). β-Alkylthio-β,γ-unsaturated alcohols were obtained in good yields by the reaction of the lithium salts with aldehydes.