Electronic effects on the stereoselectivity of epoxidation reactions catalysed by manganese porphyrins
A series of Mn(III) porphyrins progressively halogenated in the β- pyrrolic positions was employed to catalyse the epoxidation of cis-stilbene by iodosylbenzene, and to study the role of the electronic effects on the stereoselectivity of this process. A gradual improvement in the stereoselectivity on increasing the number of β-halogen atoms was observed. The role of steric effects upon the epoxidation was also investigated by placing ortho-substituents in the mesophenyl rings, and it was found that steric effects are more important than electronic effects toward the stereoselectivity of this process. These results can be rationalised by proposing a competition between a nonstereoselective electrophilic pathway of addition and a stereospecific pathway of oxygen insertion, the former being disfavoured by electron-withdrawing substituents. Alternatively, the formation of an open intermediate between the Mn(V) oxene and the substrate could be suggested, where the stereoselectivity ought to be determined by the competition between closure of the epoxide ring and rotation around the C-C bond. In this case, the enhanced stereoselectivity given by our polyhalogenated porphyrins might be attributed to an acceleration of the epoxide ring closure caused by the electron-withdrawing effect of the halogen substituents.
Publication Source (Journal or Book title)
European Journal of Organic Chemistry
Baciocchi, E., Boschi, T., Cassioli, L., Galli, C., Jaquinod, L., Lapi, A., Paolesse, R., Smith, K., & Tagliatesta, P. (1999). Electronic effects on the stereoselectivity of epoxidation reactions catalysed by manganese porphyrins. European Journal of Organic Chemistry (12), 3281-3286. https://doi.org/10.1002/(sici)1099-0690(199912)1999:12<3281::aid-ejoc3281>3.0.co;2-1