title: The vinylketene-acylallene rearrangement: theory and experiment.
abstract: Alkoxyvinylketenes4are generated by flash vacuum thermolysis (FVT) or photolysis of 3-alkoxycyclobutenones3. The thermal interconversion of4and allene carboxylic acid esters5under FVT conditions is demonstrated by Ar matrix FTIR spectroscopy. In addition, ethoxy-vinylketene4bundergoes thermal elimination of ethene with formation ofs-cis-ands-trans-acetylketene(8). An analogous aminovinylketene-to-allenecarbox-amide conversion is observed on FVT of 3-dimethylaminocyclobutenone3c. A facile 1, 3-chlorine migration in 2, 3-buta-dienoyl chloride(5d)is also reported. Consistent with the experimental observations, 1, 3-methoxy, 1, 3-chloro, and 1, 3-dimethylamino migrations in vinylketene are calculated (G2(MP2, SVP) level) to have moderate barriers of 169, 157, and 129 kJ mol(-1) , respectively, significantly less than the corresponding 1, 3-H shift barrier (273 kJ mol(-1) ). The stabilization of the four-center transition structures is rationalized in terms of the donor-acceptor interaction between the lone pair electrons of the migrating donor substituent and the vacant central carbon p orbital of the ketene LUMO. The predicted migratory aptitude in the series of substituted vinylketenes, R-C(CH2 )-CHCO, is in the order N(CH3 )2 >SCH3 >SH>Cl>NH2 >OCH3 >OH>F>H>CH3 , and correlates well with the electron-donating ability of the R group.
authors.affiliation: Department of Chemistry, The University of Queensland Brisbane, QLD 4072 (Australia), Fax: Int. code +(7)3365-4580, e-mail: wentrup@chem.chemistry.uq.edu.au.
authors.forename: H
authors.initials: H
authors.lastname: Bibas
authors.forename: M W
authors.initials: MW
authors.lastname: Wong
authors.forename: C
authors.initials: C
authors.lastname: Wentrup
keywords: ab initio calculations; allenes; ketenes; matrix isolation; rearrangements