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Computational modeling of the mechanisms and stereochemistry of circumambulatory rearrangements of formylcyclopropene and 4‐hydroxycyclobutenyl cation
Author(s) -
Minkin Vladimir I.,
Dorogan Igor V.,
Minyaev Ruslan M.
Publication year - 2000
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/(sici)1099-1395(200001)13:1<3::aid-poc201>3.0.co;2-r
Subject(s) - chemistry , intramolecular force , conformational isomerism , protonation , zwitterion , cyclobutadiene , cope rearrangement , stereochemistry , transition state , ring flip , crystallography , computational chemistry , potential energy surface , ring (chemistry) , molecule , ion , biochemistry , organic chemistry , catalysis
MP2(fc)/6‐31G** calculations on the ground and transition state structures for intramolecular rearrangements of formylcyclopropene found that circumambulation of the ring by a formyl group occurs through a high‐energy (Δ E = 42.6 kcal mol −1 ) intermediate with a structure similar to bicyclo[1.1.0]oxide zwitterion. By passing through two successive transition state structures this intermediate rearranges also to topomers of monoepoxide of cyclobutadiene (Dewar furan). Another intramolecular rearrangement of formylcyclopropene leading to inversion of stereochemical configuration at the sp 3 ‐carbon centre is associated with a one‐step transposition reaction which involves a CC bond scission. The energy barrier to the circumambulatory rearrangement of formylcyclopropene can be considerably decreased by protonation of the carbonyl group resulting in formation of the homoaromatic 4‐hydroxycyclobutenyl cation. Exo and endo conformers of this cation are susceptible to low‐energy barrier (10.1 and 10.3 kcal mol −1 , correspondingly) circumambulatory rearrangement due to migration of a hydroxymethylene group along the periphery of the three‐membered ring. The rearrangement occurs as a non‐concerted two‐step reaction involving intermediacy of bisected exo and endo conformers of hydroxycyclopropenylcarbinyl cation, and results in inversion of stereochemical configuration at the migrating carbon centre. Homoaromaticity of 4‐hydroxycyclobutenyl cation is manifested by the predicted high energy barrier (13.1 kcal mol −1 ) against its planar inversion. Copyright © 2000 John Wiley & Sons, Ltd.