Dichotomy in the reaction between cinnamyl dithiocarboxylates and tetracyanoethylene with the formation of 7,8-dithiabicyclo[3.2.1]octanes and dithioacyloxycyclopentanes

The reaction of cinnamyl dithiocarboxylates (1) containing electron-donating substituents at the central carbon atom of the dithioester group (R = p-MeOC₆H₄, EtO, andp-Tol) with tetracyanoethylene affords 2,2,3,3-tetracyano-4-endo-phenyl-7,8-dithiabicyclo[3.2.1]octanes (2) as well as isomeric 3,3,4,4-tetracyano-2-phenyl-trans-1-dithioacyloxycyclopentanes (3). Dithiabicyclooctanes2 rearrange to the corresponding cyclopentanes3 upon thermolysis.Dedicated to Academician of the RAS N. S. Zefirov (on his 60th birthday).Deceased in August, 1995.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1804–1808, September, 1995.This work was supported by the Russian Foundation for Basic Research (Project No. 93-03-04290), the International Science Foundation and the Russian Government (Grant M5Y 300), and the Russian State Committee on Higher Education (Scientific and Technical Program Fine Organic Synthesis, Project FT-12).