Sunday, 28 August 2016

organic chemistry - Which ring expansion in cyclobutyl(cyclopropyl)methanol is favourable?




Predict major product:


cyclobutyl(cyclopropyl)methanol + H+



In this question first I've protonated the OH group and then water is removed to form a carbocation. Now I have to expand the ring, but I'm confused which ring to choose: 3-membered ring or 4-membered ring?


enter image description here


Note: I can make an alkene (which would be the final product of the reaction) by removing an alpha hydrogen if it is known which ring to expand.



Answer



It is clear to me that no matter which ring you open the first, you'd get the same product as A. Michael Lautman gave the correct product , first opening the cyclopropyl ring. Michael's mechanism is fair, but I'm reluctant to say it is the most preferable path because it gives you bicyclobutyl $2^\circ$ carbocation as an intermediate, which needed extra 1,2-hydride shift to get stabilized as $3^\circ$ carbocation (total of 5 steps). However, if you have opened the cyclobutyl ring first, you'd get the same final product A, through a relatively low energy cyclopropylcyclopentane carbocation (total of 5 steps) even though it is also needed a 1,2-hydride shift (in relatively more stable cyclopentyl $2^\circ$ carbocation when compared to $2^\circ$ carbocation in cyclobytyl ring in Michael's mechanism) to get stabilized as $3^\circ$ carbocation. Complete mechanism is depicted below:


cyclobutyl(cyclopropyl)methanol


This mechanism is supported by following reference:




  • G. K. Surya Prakash, V. Prakash Reddy, G. Rasul, J. Casanova, G. A. Olah, “The Search for Persistent Cyclobutylmethyl Cations in Superacidic Media and Observation of the Cyclobutyldicyclopropylmethyl Cation,” J. Am. Chem. Soc. 1998, 120(51), 13362–13365 (https://doi.org/10.1021/ja9828962).


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