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Free-radical addition
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==With stable inorganic radicals== [[File:Self_terminating_radical_cylization,_updated.png|alt=A self-terminating radical cyclization reaction scheme|thumb|600x600px|{{vanchor|Self-terminating oxidative radical cyclization}}]] In '''self-terminating oxidative radical cyclization''', [[Inorganic compound|inorganic]] radicals oxidize [[alkyne]]s to [[ketone]]s through an [[Intramolecular reaction|intramolecular]] [[radical cyclization]]. This reaction is not catalytic, and requires the oxidized radical source in [[stoichiometry|stoichiometric]] amounts. In effect, the radical species is [[synthon|synthetically equivalent]] to [[monatomic oxygen]].<ref name="SelfTerm" /> In [[#Self-terminating oxidative radical cyclization|the paradigmatic example]], a [[nitrate]] radical (from [[photolysis]] of [[ammonium cerium(IV) nitrate|ceric ammonium nitrate]]) adds to an [[alkyne]] to generate a very reactive [[Vinyl ester|vinyl nitrate ester]] radical. The vinyl radical [[hydrogen atom transfer|abstracts an intramolecular hydrogen atom]] 5 atoms away before [[Baldwin's rules|5-''exo''-trig ring-closure]]. The resulting [[alkyl nitrate]] radical can then [[Fragmentation (chemistry)|fragment]] to a [[ketone]] and the stable radical [[nitrogen dioxide]].<ref name="SelfTerm" /> [[Sulfate]] (from [[ammonium persulfate]]) and [[hydroxyl]] radicals show similar reactivity.<ref name="SelfTerm" />
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