98752-66-0Relevant academic research and scientific papers
S(H)2' reaction in organocobaloximes: Synthesis and 1,3-rearrangement of exo-methylene alicyclic allyl sulfones
Roy,Das,Bhanuprakash,Gupta
, p. 1847 - 1858 (1994)
Photostimulated reactions of cyclopentenylmethyl-, cyclohexenylmethyl- and α-pinenyl cobaloximes with arenesulfonyl halides result in the formation of corresponding exo-methylene cycloalkylsulfones in 82-98% isolated yields. The product formation is rationalized by a radical chain mechanism involving an S(H)2' displacement of cobaloxime(II) from organocobaloximes by sulfonyl radical. Reaction under thermal condition, however, provides a mixture of exo-methylene cycloalkylsulfone and its endo-isomer. Independent experiments confirmed that the endo-isomer arises from a facile 1,3-allylic rearrangement of the exo-isomer. From mechanistic and theoretical studies the rearrangement is proposed to involve a [1,3]-sigmatropic migration of sulfonyl group.
HOMOLYTIC DISPLACEMENT AT CARBON. X. TOLUENESULPHONYL IODIDE AS A SOURCE OF TOLUENESULPHONYL RADICALS FOR THE FORMATION OF ALLYL-, BENZYL-, CYCLOPROPYLCARBINYL-, SPIROCYCLOPROPYLCYCLOALKYL-, BICYCLOALKYL-, AND BICYCLOALKYL-4-TOLYLSULPHONES FROM ORGANOCOBALOXIMES
Ashcroft, Martyn R.,Bougeard, Peter,Bury, Adrian,Cooksey, Christopher J.,Johnson, Michael D.
, p. 403 - 416 (2007/10/02)
4-Toluenesulphonyl iodide reacts thermally at alkylsulphone.Spiro- and bicyclo-alkyl compounds are also formed with other free radical precursors.The reactions are believed to take place through a chain mechanism in which cobaloxime(II), present adventitiously or formed by partial homolysis of the substrate, abstracts iodine from the toluenesulphonyl iodide to give the toluenesulphonyl radical, which attacks the organic ligand of the cobaloxime, preferably at the terminal olefinic carbon, thereby displacing cobaloxime(II) and giving the observed organic product.
