Abstract
AbstractInternally‐bridged octaphyrin(1.1.1.1.1.1.1.1) underwent a rearrangement to meso‐meso linked porphyrin dimer as a new metamorphosis. Extensive examination suggests that hydride‐addition is a key step for the rearrangements to afford thermodynamically more stable porphyrin framework. Further, β‐tetrabromo[36]octaphyrin was transformed to meso‐meso, β‐β, β‐β triply linked porphyrin dimer via a similar mechanism combined with Pd‐mediated reductive homocoupling.
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