Mechanism of transannular iodination of 3,7-dimethylenebicyclo[3.3.1]nonane derivatives

The reactions of 3,7-dimethylenebicyclo[3.3.1]nonane, norbornadiene and cis,cis-1,5-cyclooctadiene with pentafluoro-λ6-sulfanyl chloride

“…1). This mechanism is well known for many Ad E reactions of bicyclo[3.3.1]nonane dienes with electrophilic agents [24][25][26][27][28]. We suppose, that molecular chlorine was formed by recombination of chlorine atoms or reaction of Cl and SF 5 Cl.…”

“…Convenient and selective preparations of functional derivatives of adamantane and noradamantane are based on transannular cyclizations of bicyclo[3.3.1]nonane dienes with electrophilic [24][25][26][27][28] or radical agents [29][30][31]. The transannular cyclizations of norbornadiene with electrophilic and radical reagents [32][33][34][35][36] are used for selective preparation of nortricyclane derivatives.…”

Synthesis of 1,2-Disubstituted Adamantane Derivatives by Construction of the Adamantane Framework

“…The exposure of starting materials 28 to bromine or iodine forms a charge transfer complex 29 by attacking the less substituted methylene group, due to stereo-electronic factors, followed by synchronous cyclization to form the stable 1-adamantyl cation ion pair 30, leading to the products 31. Reactions were not carried out for preparative purposes; therefore, no yields were reported [56,57]. Scheme 8.…”