19930-93-9

Upstream product

• 78-85-3 2-methylpropenal 
• 28000-59-1 α,α-diiodotoluene 
• 87362-76-3 ((Z)-3-Methyl-buta-1,3-dienylsulfanylmethyl)-benzene 
• 4030-10-8 methyl-4-phenyl-2-dihydro-2,3 furanne 
• 87362-85-4 [(1R,2R)-2-Methyl-2-((Z)-2-methylsulfanyl-vinyl)-cyclopropyl]-benzene 
• 201230-82-2 carbon monoxide 
• 29817-09-2 1-methylene-2-phenylcyclopropane 
• 100-52-7 benzaldehyde 

Relevant academic research and scientific papers

α-Tetrasubstituted Aldehydes through Electronic and Strain-Controlled Branch-Selective Stereoselective Hydroformylation

Hydroformylation utilizes dihydrogen, carbon monoxide, and a catalyst to transform alkenes into aldehydes. This work applies chiral bisdiazaphospholane (BDP)- and bisphospholanoethane-ligated rhodium complexes to the hydroformylation of a variety of alkenes to produce chiral tetrasubstituted aldehydes. 1,1′-Disubstituted acrylates bearing electron-withdrawing substituents undergo hydroformylation under mild conditions (1 mol % of catalyst/BDP ligand, 150 psig gas, 60 °C) with high conversions and yields of tetrasubstituted aldehydes (e.g., 13:1 regioselectivity, 85% ee, and 99% regioselectivity and >19:1 diastereoselectivity to tetrasubstituted aldehydes at rates >50 catalyst turnovers/hour. NMR studies of the noncatalytic reaction of HRh(BDP)(CO)2 with methyl 1-fluoroacrylate enable interception of tertiary alkylrhodium intermediates, demonstrating migratory insertion to acyl species is slower than formation of secondary and primary alkylrhodium intermediates. Overall, these investigations reveal how the interplay of sterics, electronics, and ring strain are harnessed to provide access to valuable α-tetrasubstituted aldehyde synthetic building blocks by promoting branched-selective hydroformylation.

Aryl(chloro)methyl 4-tolyl sulfoxides: Synthesis and application to the synthesis of α-aryl ketones

Aryl(chloro)methyl 4-tolyl sulfoxides were synthesized from arylmethyl 4-tolyl sulfoxides in moderate-to-good yields by sequential treatment with lithium diisopropylamide and tosyl chloride at low temperatures. Treatment of the lithium α-sulfinyl carbanion of the aryl(chloro)methyl 4-tolyl sulfoxides with aldehydes or ketones resulted in the formation of adducts in good-to-high yields. Treatment of these adducts with tert-butylmagnesium chloride gave the corresponding magnesium alkoxides. On treatment with isopropylmagnesium chloride, the alkoxides gave the corresponding magnesium β-oxido carbenoids, which rearranged to give α-aryl ketones in good-to-high yields. The magnesium enolate intermediates generated by rearrangement of the -oxido carbenoids could also be trapped with electrophiles to give α-aryl α-substituted ketones. These procedures offer a good method for the synthesis of a variety of α-aryl ketones from aldehydes and ketones. Georg Thieme Verlag Stuttgart. New York.

Reaction of α-halo organoindium reagents with carbonyl compounds and electron-deficient alkenes

A variety of α-halo organoindium reagents were prepared in situ from the reaction of gem-dihalo compounds with indium metal, and their reactions with carbonyl compounds and electron-deficient alkenes were examined. The reactions of simple 1,1-diiodoalkanes with indium metal gave no defined products but benzal iodide gave stilbene in a moderate yield. α-Halo organoindium reagents derived from α,α-dibromo carbonyl compounds gave oxiranes and cyclopropanes upon the reactions with aldehydes and alkenes, respectively. 3,3-Dichloropropenes reacted with aldehydes in the presence of indium metal to give the corresponding chlorohydrins and/or homoallylalcohols, depending on the structures of both the dichloropropenes and aldehydes employed.

STEREOSELECTIVE CONVERSION OF LITHIATED BENZYLIC OR ALLYLIC 3-METHYL-1(Z),3-BUTADIENYL SULFIDES INTO CIS-DISUBSTITUTED CYCLOPROPANE COMPOUNDS

The lithio-thiacyclohexenes 6 are intermediates in the title conversion 4 9.