97597-31-4

Upstream product

• 108-94-1 cyclohexanone 
• 57213-26-0 1-(2-oxo-2-phenylethyl)cyclohexanol 
• 5452-52-8 2-cyclohexylidene-1-phenyl-1-ethanone 
• 13735-81-4 1-styrenyloxytrimethylsilane 
• 3561-67-9 bis(phenylthio)methane 
• 100-52-7 benzaldehyde 
• 253797-51-2 1-[(2-hydroxy-2-phenyl-1-phenylsulfanyl)ethyl]cyclohexanol 
• 23904-33-8 (iodomethylene)cyclohexane 

Relevant academic research and scientific papers

Asymmetric transfer hydrogenation of unsaturated ketones; factors influencing 1,4- vs 1,2- regio- and enantioselectivity, and alkene vs alkyne directing effects

A detailed study has been completed on the asymmetric transfer hydrogenation (ATH) of a series of enones using Ru(II) catalysts. Electron-rich rings adjacent to the C[dbnd]O group reduce the level of C[dbnd]O reduction compared to C[dbnd]C. The ATH reaction can readily discriminate between double and triple bonds adjacent to ketones, reducing the double bond but leaving a triple bond intact in the major product.

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.

Methane-derived polyanionic synthons from bis(phenylthio)methane

Successive treatment of bis(phenylthio)methane (1) with (a) n-butyllithium at 0°C, (b) a carbonyl compound [(t)BuCHO, Me2CO, Et2CO, (CH2)5CO] at -40°C, (c) lithium and a catalytic amount of DTBB (5%) and (d) a s

Coupling reaction of vinyl halides with ketones or aldehydes mediated by samarium diiodide

The Barbier- or Grignard-type reaction of vinyl iodides with ketones or aldehydes proceeds on treatment with samarium diiodide in benzene containing hexamethylphosphoric triamide (HMPA) to afford the corresponding coupling compounds (allyl alcohols). The reaction was shown to involve vinyl samariums as an intermediate.