“…Phenyl vinyl sulfide reacts with tropone regiospecifically to provide bicyclo[3.2.2]nonadienone systems (eq 4), 21 reacts with pyrone sulfoxide 22 with high diastereoselectivity under high pressure (eq 5), has trapped the transient [1,5]-sigmatropic shift isomer of isodicyclopentanediene, 3 and undergoes photosensitized electron transfer (PET) initiated cycloaddition 23 with dienes to give Diels-Alder products (eq 6). The resulting sulfides of these adducts have been cleaved to the corresponding alkanes, 3 oxidized to the sulfoxides followed by thermolysis to give the corresponding alkenes, 22 and oxidized to the sulfones followed by αhydroxylation to give the corresponding ketones. 23 Phenyl vinyl sulfide participates in 1,3-dipolar cycloadditions with 2-azaallyl anions, generated from N-(tributylstannyl) methanimines and n-BuLi, to provide substituted pyrrolidines (eq 7) 4 and highly stabilized isoquinolium methylides, 24 and also undergoes thiyl-radical catalyzed chain cyclizations to give methylenecyclopentanes.…”