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Although difficult, a strong Lewis acid catalyst can produce HETEROLYTIC cleavage in alkanes.
That reaction leads to unstable carbocations whose unstability diminishes with branching.
In order to achieve the minimum unstability, both hydrogens and alkyl group can 'migrate' or 'rearrange' to give the most possible substituted carbocations, i.e. the least unstable ones.

Alkane isomerization utilizes catalysts whose search is too the subject of active investigations.