text: The intramolecular Heck reaction may be used to form rings of a variety of sizes and topologies. β-Hydride elimination need not be the final step of the reaction, and tandem methods have been developed that involve the interception of palladium alkyl intermediates formed after migratory insertion by an additional reactant. This section discusses the most common ring sizes formed by the intramolecular Heck reaction and some of its tandem and asymmetric variants.
  5-Exo cyclization, which establishes a five-membered ring with an exocyclic alkene, is the most facile cyclization mode in intramolecular Heck reactions. In this and many other modes of intramolecular Heck cyclization, annulations typically produce a cis ring juncture.
  6-Exo cyclization is also common. The high stability of Heck reaction catalysts permits the synthesis of highly strained compounds at elevated temperatures. In the example below, the arene and alkene must both be in energetically unfavorable axial positions in order to react.
  Endo cyclization is observed most often when small or large rings are involved. For instance, 5-endo cyclization is generally preferred over 4-exo cyclization. The yield of endo product increases with increasing ring size in the synthesis of cycloheptenes, -octenes, and -nonenes.
  Tandem reactions initiated by IMHR have been extensively explored. Palladium alkyl intermediates generated after migratory insertion may undergo a second round of insertion in the presence of a second alkene (either intra- or intermolecular). When dienes are involved in the intramolecular Heck reaction, insertion affords π-allylpalldium intermediates, which may be intercepted by nucleophiles. This idea was applied to a synthesis of (–)-morphine.
  Asymmetric IMHR may establish tertiary or quaternary stereocenters. BINAP is the most commonly chiral ligand used in this context. An interesting application of IMHR is group-selective desymmetrization (enantiotopic group selection), in which the chiral palladium aryl intermediate undergoes insertion predominantly with one of the enantiotopic double bonds.