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Ring expansion from a given cyclic carbocation
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+ Biochemistry
+ Rearrangements
+ Carbocation
+ Stability
Posted by
Neil Farbstein
Ring expansion from a given cyclic carbocation
I think your friend is thinking of the cyclobutyl carbocation which does ring contract to the cycylopropyl carbinyl carbocation (and also equilibrates with the methallyl carbocation).
However, just as you thought, the cyclobutyl carbinyl carbocation does ring open to the cyclopentyl carbocation (ref_1, ref_2, ref_3). This rearrangement is driven by carbocation stability (primary to secondary) and relief of the steric strain present in the 4-membered ring, again, just as you suggested.
Note: this question has been asked previously on SE Chem, however I believe the accepted answer is incorrect, as it seems to primarily address the cyclopropyl carbinyl case, and what is said about the cyclobutyl carbinyl carbocation (little to no ring expansion) is incorrect.
I think your friend is thinking of the cyclobutyl carbocation which does ring contract to the cycylopropyl carbinyl carbocation (and also equilibrates with the methallyl carbocation).
However, just as you thought, the cyclobutyl carbinyl carbocation does ring open to the cyclopentyl carbocation (ref_1, ref_2, ref_3). This rearrangement is driven by carbocation stability (primary to secondary) and relief of the steric strain present in the 4-membered ring, again, just as you suggested.
Note: this question has been asked previously on SE Chem, however I believe the accepted answer is incorrect, as it seems to primarily address the cyclopropyl carbinyl case, and what is said about the cyclobutyl carbinyl carbocation (little to no ring expansion) is incorrect.
The point would be that under QM, in either case, the charge will not wholly be on one carbon. That said, I ran a high-level CCSD calculation and its pretty localized on the primary (as you drew): More
What would you think is more stable from the species $\ce{C4H7+}$, the cyclopropylmethylium (that you drew) or the methylcyclopropan-1-ylium? I tend to think the latter, but I am absolutely not certain.More
I think your friend is thinking of the cyclobutyl carbocation which does ring contract to the cycylopropyl carbinyl carbocation (and also equilibrates with the methallyl carbocation).
However, just as you thought, the cyclobutyl carbinyl carbocation does ring open to the cyclopentyl carbocation (ref_1, ref_2, ref_3). This rearrangement is driven by carbocation stability (primary to secondary) and relief of the steric strain present in the 4-membered ring, again, just as you suggested.
Note: this question has been asked previously on SE Chem, however I believe the accepted answer is incorrect, as it seems to primarily address the cyclopropyl carbinyl case, and what is said about the cyclobutyl carbinyl carbocation (little to no ring expansion) is incorrect.
I think your friend is thinking of the cyclobutyl carbocation which does ring contract to the cycylopropyl carbinyl carbocation (and also equilibrates with the methallyl carbocation).
However, just as you thought, the cyclobutyl carbinyl carbocation does ring open to the cyclopentyl carbocation (ref_1, ref_2, ref_3). This rearrangement is driven by carbocation stability (primary to secondary) and relief of the steric strain present in the 4-membered ring, again, just as you suggested.
Note: this question has been asked previously on SE Chem, however I believe the accepted answer is incorrect, as it seems to primarily address the cyclopropyl carbinyl case, and what is said about the cyclobutyl carbinyl carbocation (little to no ring expansion) is incorrect.
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