32789-43-8

Upstream product

• 32789-43-8 cis 2-methyl-3-benzoylcyclohexanone 
• 1121-18-2 2-methyl-2-cyclohexen-1-one 
• 827-36-1 2-(N,N-dimethylamino)-2-phenylacetonitrile 
• 930-68-7 cyclohexenone 
• 74-88-4 methyl iodide 
• 67755-90-2 Ethoxy-1-ethoxy-(phenyl)-acetonitrile 
• 70719-02-7 C₁₂H₁₄NO₂^(1-)*Li⁽¹⁺⁾ 
• 94517-07-4 Dimethylamino-((1R,2R)-2-methyl-3-oxo-cyclohexyl)-phenyl-acetonitrile 

Downstream Products

• 32789-43-8 1-Benzoyl-6-methylcyclohexanon-⁽⁵⁾ 

Relevant academic research and scientific papers

Photoredox-Catalyzed Isomerization of Highly Substituted Allylic Alcohols by C?H Bond Activation

Photoredox-catalyzed isomerization of γ-carbonyl-substituted allylic alcohols to their corresponding carbonyl compounds was achieved for the first time by C?H bond activation. This catalytic redox-neutral process resulted in the synthesis of 1,4-dicarbonyl compounds. Notably, allylic alcohols bearing tetrasubstituted olefins can also be transformed into their corresponding carbonyl compounds. Density functional theory calculations show that the carbonyl group at the γ-position of allylic alcohols are beneficial to the formation of their corresponding allylic alcohol radicals with high vertical electron affinity, which contributes to the completion of the photoredox catalytic cycle.

AMINONITRILE AND CYANOHYDRIN ETHERS AS BENZOYL ANION EQUIVALENTS IN CONJUGATE ADDITIONS TO SUBSTITUTED α CYCLENONES : COMPARATIVE SYNTHETIC POTENTIALITIES

Lithiated aminonitrile 1a and cyanohydrin ether 2a are good nucleophilic benzoyl equivalents in conjugate addition to α cyclenones. 1a is more sensitive to β substitution of the cyclenone than 2a, as in THF it does not react with 3-methyl substituted cycl

REACTIVITE DE LITHIENS DERIVES D'ETHERS DE LA CYANHYDRINE DU BENZALDEHYDE VIS-A-VIS D'α-ENONES CYCLIQUES

Conjugate addition of reagent 1A to 2-cyclohexenone 3 can be realized in THF-HMPT, so that one-pot conjugate addition - CH3I enolate trapping, leading to trans 2-methyl 3-benzoylcyclohexanone 17 can be easily performed.From isophorone 4 and Δ1(9)-2-octalone 5, 1,4-addition under kinetic control is observed in THF.In the presence of HMPA, the reaction is under thermodynamic control.At low temperatures enolate 19a is in equilibrium with 1A and 4; from 4 at 0 deg C or 5 at -65 deg C or at 0 deg C, the equilibrium lies on the side of starting materials.No reaction between 1A and 6 takes place in any solvent.The reaction of 1B and isophorone 4 in THF leads to 1,2-addition under kinetic control and to 1,4-addition under thermodynamic control.In THF-HMPT, retro-Michael addition is observed.However, 1,2-addition takes place in THF to 6. The different results are interpreted in terms of interplay of ion-pairing, steric decompression and steric hindrance to 1,4-addition as well as the possibility of participation of the Li cation for 1,2-addition.

ADDITION CONJUGUEE D'AMINONITRILES, EQUIVALENTS DE BENZOYLE, AUX CYCLENONES. QUELQUES EXEMPLES DE SYNTHESES STEREOSELECTIVES DE CYCLANONES 2,3-DISUBSTITUEES CIS.

Conjugate addition of benzoyl anion equivalents to unsubstituted and 2-substituted cyclenones is proved in some cases to be highly stereoselective.Cis 2-methyl 3-benzoyl cyclanones are obtained with excellent yields.