Dipole moments of arylcis- andtrans-styryl sulphides and sulphones

Baliah, V.; Rathinasamy, T. K.

doi:10.1007/bf02841064

Cited by 1 publication

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References 8 publications

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“…Reaction of 1c with 2 and 14. After 30 h, column chromatography of the reaction mixture afforded a mixture of 4c , 5c , and 6 in a 1 (two isomers in a 1:1 ratio):1:0.8 ratio (25% overall yield). 5c : MS m / z 240 (M + , 100); HRMS calcd for C 15 H 12 OS 240.0608, found 240.0618.…”

Section: Methodsmentioning

confidence: 99%

Radical Addition to Isonitriles: A Route to Polyfunctionalized Alkenes through a Novel Three-Component Radical Cascade Reaction

2000

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The reaction of aromatic disulfides, alkynes, and isonitriles under photolytic conditions affords polyfunctionalized alkenes--beta-arylthio-substituted acrylamides or acrylonitriles--in fair yields through a novel three-component radical cascade reaction. The procedure entails addition of a sulfanyl radical to the alkyne followed by attack of the resulting vinyl radical to the isonitrile. A fast reaction, e.g., scavenging by a nitro derivative or beta-fragmentation, is necessary in order to trap the final imidoyl radical, since addition of vinyl radicals to isonitriles seems to be a reversible process. The stereochemistry of the reaction is discussed, particularly with respect to the stereochemical outcome of related hydrogen abstraction reactions by the same vinyl radicals. The lower or even inverted preference for either geometrical isomer observed in our cases with respect to that encountered in hydrogen abstraction reactions is explained in terms of transition-state interactions and/or isomerization of the final imidoyl radical. The latter possibility is supported by semiempirical calculations, which show that the spin distribution in the imidoyl radical can allow rotation of the adjacent carbon-carbon double bond prior to beta-fragmentation.

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Section: Methodsmentioning

confidence: 99%