Saturday, November 18, 2017

organic chemistry - Determination of products in reactions involving carbocation rearrangement?


How do you determine the migratory "aptitude" of various groups during carbocation rearrangements? Is there a experimentally determined order?
For example, what will be the product in case of the following pinacol-pinacolone type rearrangement: $$\ce{(cyclo-pentyl)CH3C(OH)-C(OH)(CH3)(cyclo-pentyl) ->products}$$


Will the methyl group be transferred or the cyclopentyl moiety? The same question arises if the cyclopentyl is replaced with phenyl group? In general, which shifts, methyl, hydrogen, phenyl or any other group, will take place? Or equivalently, what determines which group has a greater tendency to undergo shifts during carbocation rearrangements?




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