33475-09-1

Upstream product

• 4685-47-6 3,4-dimethylanisole 
• 43087-42-9 4-methoxy-1,2-dimethyl-1,4-cyclohexadiene 
• 73301-14-1 1-phenylsulfonyl-3,4-dimethylcyclohex-3-ene 
• 17351-28-9 1,2-dimethyl-1,4-cyclohexadiene 
• 173416-86-9 4,5-dimethyl-1-phenylseleno-2-(p-toluenesulfonyl)-1,4-cyclohexadiene 
• 249540-13-4 1-(2-methoxy-4,5-dimethyl-cyclohexa-1,4-dienesulfonyl)-4-methyl-benzene 
• 513-81-5 2,3-dimethyl-buta-1,3-diene 
• 249540-15-6 3,4-dimethyl-6-(toluene-4-sulfonyl)-cyclohex-3-enone 

Downstream Products

• 1007347-77-4 4-(4-methoxyphenyl)-3,4-dimethylcyclohex-2-enone 
• 89162-97-0 (R)-(+)-3,4-dimethyl-2-cyclohexen-1-one 
• 474094-60-5 (S)-(-)-3,4-dimethyl-2-cyclohexen-1-one 
• 53829-24-6 1,2-dimethyl-1-cyclohexen-4-yl tosylate 
• 31617-49-9 3,4-dimethyl-1-morpholino-1,3-cyclohexadiene 
• 53829-23-5 3,4-dimethylcyclohex-3-enol 
• 10463-42-0 3,4-dimethyl-cyclohex-2-enone 
• 1619-28-9 3-isopropyl-cyclopent-2-enone 

Relevant academic research and scientific papers

Asymmetric approach toward chiral cyclohex-2-enones from anisoles via an enantioselective isomerization by a new chiral diamine catalyst

A 3-step asymmetric approach toward the optically active chiral cyclohex-2-enones from anisoles has been developed. The crucial asymmetric induction step is an unprecedented catalytic enantioselective isomerization of β,γ-unsaturated cyclohex-3-en-1-ones

Cycloaddition Reactions of 1-Phenylseleno-2-(p-toluenesulfonyl)ethyne

1-Phenylseleno-2-(p-toluenesulfonyl)ethyne (1) is an effective dienophile and dipolarophile. It underwent facile Diels-Alder reactions with a variety of dienes to afford vicinal sulfone- and selenide-functionalized 1,4-cyclohexadienes. Unexpected regiochemistry that is the opposite of what is obtained with simple acetylenic sulfones was observed with several unsymmetrical dienes containing methyl or methoxy substituents at the 1- or 2-position. Acetylene 1 reacted with (trimethylsilyl)methyl azide, diazomethane, and 2,4,6-trimethylbenzonitrile N-oxide via 1,3-dipolar cycloadditions to afford the corresponding triazole, 1,2-diazole, and isoxazole products. It also underwent an ene reaction with β-pinene that showed anomalous regiochemistry compared to other acetylenic sulfones. The Diels-Alder cycloadducts obtained from the reaction of 1 with 2,3-dimethyl-1,3-butadiene and 1,3-cyclohexadiene were readily converted into the corresponding β-keto sulfones and ketones, thus rendering 1 as the synthetic equivalent of p-toluenesulfonylketene and ketene, respectively. Base-catalyzed elimination of TsOH from the Diels-Alder cycloadduct obtained with 2,3-dimethyl-1,3-butadiene afforded the corresponding aryl phenyl selenide, while the adduct from piperylene underwent oxidation to its selenoxide, followed by a Pummerer-type reaction to produce 2-(phenylseleno)-3-(p-toluenesulfonyl)toluene. The reaction of the bicyclic Diels-Alder product obtained from 1,3-cyclohexadiene with MeCu(SePh)Li resulted in substitution of the phenylseleno moiety by a methyl group, whereas similar treatment of the monocyclic adduct derived from piperylene effected elimination of PhSeH and aromatization.

trans-Bis(5-alkoxy- and 5-hydroxy-1-3-η3-cyclohexenyl)palladium Complexes by Palladium(II)-Promoted Addition of Alcohols and Water to 1,2-Dialkyl-1,4-cyclohexadienes

Aliphatic alcohols and water add to 1,2-dialkyl-1,4-cyclohexadienes in the presence of bis(acetonitrile)palladium dichloride to form trans-bis(5-alkoxy- and 5-hydroxy-1,2-dialkyl-1-3-η3-cyclohexenyl)palladium chloride complexes, respectively.In the alcohol series, the reaction is sensitive to the steric bulk of the alcohol nucleophile.To demonstrate synthetic utility, the derived palladium complexes in the water series were regioselectively and stereoselectively converted by subsequent methoxycarbonylation to the corresponding methyl trans-5-hydroxy-2,3-dialkyl-2-cyclohexene-1-carboxylates.

Factors Influencing Conformational Preferences in Cyclohexenes

Conformational preferences have been measured for the first time for 4-substituted cyclohexenes in a solvent of low polarity.Measurements were made for the substituents Cl, Br, I, OH, OSiMe3, and CN and were compared with conformational preferences in cyclohexyl and exo-methylenecyclohex-3-yl.In the nearly nonpolar solvent CF2Cl2, in which intramolecular interactions are maximized, there is a much larger axial population for cyclohexen-4-yl than in cyclohexyl or exo-methylenecyclohex-3-yl.In particular, the dipolar interaction of the endocyclic double bond is reduced from that of the exocyclic double bond.This observation is confirmed by the almost negligible effect of symmetrizing the endocyclic double bond through 1,2-dimethyl substitution, in contrast with the large effect of symmetrizing the exocyclic double bond through 7,7-dimethyl substitution.Polar solvents increase the proportion of the axial conformer to a smaller extent for the endocyclic than for the exocyclic system, again in agreement with a lower dipolar effect in the endocyclic case.These results emphasize the anisotropic nature of the steric effects of double bonds.

OXIDATIVE DESULFONYLATION. PHENYL VINYL SULFONE AS A KETENE SYNTHETIC EQUIVALENT

α-Sulfonyl carbanions undergo oxidative desulfonylation to form ketones upon treatment with molybdenum peroxide MoO5*Py*HMPA (MoOPH) in THF at -78 deg C.