Thiyl radicals regioselectivity

Ferreri C, Samadi A, SassateUi F, Landi L, Chatgilialoglu C. (2004) Regioselective cis-trans isomerization of arachidonic double bonds by thiyl radicals The influence of phospholipid supramolecular organization. / Aw Chem Soc 126 1063-1072. 

The concept of ring opening of cyclopropylcarbinyl radicals has been extended to substituted methylenecyclopropanes. As shown in Scheme 4, the crucial step in the reaction sequence is the regioselective addition of a substituted thiyl radical. After opening of the cyclopropane ring, the resulting radical adds to the olefin. Subsequent cyclization and reductive regeneration of the thiyl radical with concomitant liberation of the methylenecyclopentane product complete this transformation [6]. 

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