Synthesis of Cyclic Ketones by Electrochemical Reduction ofS-(2-Methoxycarbonyl)phenyl Thiolesters

Facile New Syntheses of Substituted Benzhydryl Derivatives Using Trichloroacetimidate C-C Bond Formation Method

“…Winthrop & Humber [34] earlier described the synthesis of 2-benzhydrylcyclohexanone 8 by the reaction of benzylidenecyclohexanone with phenyl Grignard reagent in the presence of cuprous chloride and trichloroacetic acid as a solvent yielded 35 % 8. Also 2-benzhydrylcyclohexanone 8 could be obtained in 61 % yield as reported by electroreduction of S-(2-methoxycarbonyl)-phenyl 5-hexene or 6-heptene thioates in an undivided cell containing tetraethylammonium perchlorate (TEAP), graphite plate and an aluminum rod as supporting electrolyte, cathode and anode, respectively [35]. The reaction of an excess of phenyllithium or phenylmagnesium bromide with either cisor trans-styryl cyanide gives 1-benzhydryl 2-phenyl 2ethanone 10 in 7 % yield and the known isomer of benzalacetophenone in 34 % yield [32].…”

Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance

“…This process was shown to generate an acyl radical which could cyclize onto pendant olefins to forge cyclic ketones. 625 …”

Organolead‐Mediated Arylations: 2‐(3,3‐Diphenylallyloxy)phenyllead Triacetate as an Internal Free‐Radical‐Trap‐Containing Reagent

“…Examples of internal trapping of free-radical species on such a gem-diphenylethene group have been reported by Newcomb et al in the case of α-ethoxycarbonyl and α-cyano free radicals, [21] nitrogen-centred radicals [22] and more recently by Ozaki et al [23] in the case of electrochemically generated acyl radicals. Kinetic studies showed a rate constant of 4.5 ϫ 10 7 s Ϫ1 for the cyclisation of the 6,6-diphenylhex-5-enyl radical [24] compared to a rate of 2.7 ϫ 10 5 s Ϫ1 for the cyclisation of the unsubstituted hex-5-enyl radical.…”