Oxidation of 2-Alkylcycloalkanones with Iodine–Cerium(iv) Salts in Alcohols

Copper-Assisted Direct Nitration of Cyclic Ketones with Ceric Ammonium Nitrate for the Synthesis of Tertiary α-Nitro-α-substituted Scaffolds

“…Initially, we selected commercially available 2-phenylcyclohexanone as a model substrate to test our designed nitration using CAN as a multifunctional reagent. However, competitive side reactions needed to be suppressed, such as the nitration of the C­(sp 2 )–H bond on the phenyl ring, the formation of benzyl nitrates, the cleavage of the C–C bond at the ketone α-position, and the self-coupling of 2-phenylcyclohexanone . After some attempts, to our delight, the desired product 2a was isolated in 43% yield when the reaction was performed in 1,2-dichloroethane (DCE) at 80 °C for 12 h (entry 1).…”

Esterification of Alkene with Cerium(IV) Sulfate in Carboxylic Acid

“…6 Still earlier, we reported that the reaction of cycloalkenes with iodine-cerium(IV) sulfate (CS) in acetonitrile-water (10:1) at 50°C, yielded trans-iodohydrins preferentially 7 and the reaction of styrene derivatives with CS in methanol yielded 1,2-dimethoxy compounds. 8 We now report that the reaction of alkenes [cyclohexene (1), cycloheptene (2), cyclooctene (3), 1-heptene (4), 1-octene (5), styrene (6), 1,7-octadiene (7), indene (8), and 1,2dihydronaphthalene ( 9)] with CS in carboxylic acids gave the corresponding carboxylic esters in good yields. These results are summarised in Table 1.…”

Reaction of α,β‐unsaturated ketones with cerium(IV) salts in alcohol

“…7 In previous work, we have reported a novel α-iodination of ketones to afford the corresponding iodo ketones; 8,9 a new alkoxyiodination and nitratoiodination of olefins; 10,11 new oxidative aromatization of α,β-unsaturated cyclohexenones; 12 and a new α,α -diiodination of ketones using iodine-ammonium cerium(IV) nitrate (CAN). 13 Still earlier, we described oxidation of 2-substituted cycloalkanones with cerium(IV) sulfate tetrahydrate (CS) in alcohols and acetic acid; 14,15 cerium(IV) sulfate mediated oxidative addition of 1-phenylcycloalkenes and styrene derivatives in methanol for synthesis of 1,2-dimethoxy compound; 16 preparative conversion of oxime to parent carbonyl compounds by cerium(IV) sulfate in acetonitrile and alcohol;…”