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Decarbonylative rearrangement of seleno‐ and tellurocarbamates carrying an allenyl group on the nitrogen was found to proceed in the presence of a palladium catalyst to afford 3‐chalcogeno‐1‐azadienes. This transformation may involve oxidative addition of Pd to a carbon–chalcogen bond, decarbonylation from a carbamoylpalladium unit (R2N‐C(O)‐PdChPh: Ch = Se or Te), Pd shift, and reductive elimination.
α‐(Phenyltelluro)esters 2 reacted with electron‐rich alkenes 3 in the presence of a catalytic amount of azobisisobutyronitrile (AIBN) as an initiator to give the corresponding addition products 4. This carbotelluration of alkenes proceeded via a radical chain mechanism involving the bimolecular homolytic substitution (SH2) reaction on tellurium as the key step, wherein tellurium plays an important...
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