6286-53-9

Upstream product

• 5153-67-3 nitrostyrene 
• 78-79-5 isoprene 
• 21889-89-4 2,3-epoxy-3-methylcyclohexanone 
• 23402-69-9 lithium diphenylcuprate 
• 77326-15-9 2,3-epoxy-3-methyl-1-(trimethylsiloxy)-6-cyclohexene 
• 838826-71-4 4-methyl-1-phenyl-5-hexen-2-one 
• 77326-15-9 Trimethyl-(6-methyl-7-oxa-bicyclo[4.1.0]hept-2-en-2-yloxy)-silane 

Downstream Products

• 5662-73-7 α-phenyl-δ-oxocaproic acid 

Relevant academic research and scientific papers

Vinylcyclopropylacyl and polyeneacyl radicals. Intramolecular ketene alkyl radical additions in ring synthesis

Treatment of a variety of substituted vinylcyclopropyl selenyl esters, e.g. 11, with Bu3SnH-AIBN in refluxing benzene leads to the corresponding acyl radical intermediates, which undergo rearrangement and intramolecular cyclisations via their ketene alkyl radical equivalents producing cyclohexenones in 50-60% yield. By contrast, treatment of conjugated triene selenyl esters, e.g. 32, with Bu3SnH-AIBN produces substituted 2-cyclopentenones via intramolecular cyclisations of their ketene alkyl radical intermediates. Under the same radical-initiating conditions the selenyl esters derived from o-vinylbenzoic acid and o-vinylcinnamic acid undergo intramolecular cyclisations producing 1-indanone and 5,6-dihydrobenzocyclohepten-7-one respectively in 60-70% yields. A tandem radical cyclisation from the α,β,γ, δ-diene selenyl ester 31 provides an expeditious synthesis of the diquinane 35 in 69% yield.

Palladium-catalyzed intramolecular hydroalkylation of alkenyl- β-keto esters, α-aryl ketones, and alkyl ketones in the presence of Me 3SiCl or HCI

Reaction of 3-butenyl β-keto esters or 3-butenyl α-aryl ketones with a catalytic amount of [PdCl2(CH3CN)2] (2) and a stoichiometric amount of Me3SiCl or Me3SiCl/ CuCl2 in dioxane at 25-70°C formed 2-substituted cyclohexanones in good yield with high regioselectivity. This protocol tolerated a number of ester and aryl groups and tolerated substitution at the allylic, enolic, and cis and trans terminal olefinic positions. In situ NMR experiments indicated that the chlorosilane was not directly involved in palladium-catalyzed hydroalkylation, but rather served as a source of HCl, which presumably catalyzes enolization of the ketone. Identification of HCl as the active promoter of palladium-catalyzed hydroalkylation led to the development of an effective protocol for the hydroalkylation of alkyl 3-butenyl ketones that employed sub-stoichiometric amounts of 2, HCl, and CuCl2 in a sealed tube at 70°C.

Vinylcyclopropylacyl Radicals. Intramolecular Ketene Additions leading to Concise Syntheses of Cyclohexenones

Treatment of a range of vinylcyclopropyl selenyl esters with Bu3SnH-AIBN produces cyclohexenone products (50-60%) via 6-exo-dig radical cyclisations involving ketene intermediates.