Peroxy acid epoxidation of acyclic allylic alcohols. Competition between s-trans and s-cis peroxy acid conformers.
[Reaction: see text]. RB3LYP calculations, reported here, indicate that peroxy acid s-cis conformer is more stable than its s-trans counterpart, in agreement with experimental data. Difference in stability is the highest in the gas phase, but it falls considerably on going from the gas phase to moderately polar solvent. In the case of peroxy formic acid, the enthalpy (free energy) difference is about 3.4 (2.5) kcal/mol, respectively, in the gas phase but decreases to 1.2 (0.6) kcal/mol in dichloromethane solution. Introduction of an alkyl or aryl substituent on the peroxy acid, that is, on passing to peroxy acetic, peroxy benzoic (PBA), and m-chloroperoxy benzoic acid (MCPBA), adds a further significant (1.0-1.5 kcal/mol) favor to the s-cis isomer. RB3LYP/6-31+G(2d,p) calculations on the epoxidation of 2-propenol with peroxy formic and peroxy benzoic acids, respectively, suggest that the less stable peroxy acid s-trans conformer can compete with the more stable s-cis form in epoxidation reaction of these substrates. Transition structures arising from s-trans peroxy acids ("trans" TSs) retain both the well-established, for "cis" TS, perpendicular orientation of the O-H peroxy acid bond relative to the C=C bond and the one-step oxirane ring formation. These TSs collapse to the final epoxide via a 1,2-H shift at variance with the 1,4-H transfer of the classical Bartlett's "cis" mechanism. The "trans" reaction pathways have a higher barrier in the gas phase than the "cis" reaction channels, but in moderately polar solvents they become competitive. In fact, the "trans" TSs are always significantly more stabilized than their "cis" counterparts by solvation effects. Calculations also suggest that going from peroxy formic to peroxy benzoic acid should slightly disfavor the "trans" route relative to the "cis" one, reflecting, in an attenuated way, the decrease in the peroxy acid s-trans/s-cis conformer ratio. The predicted behavior for MCPBA parallels that of PBA acid.
Freccero
Mauro
M
Dipartimento di Chimica Organica, Università di Pavia, V.le Taramelli 10, 27100 Pavia, Italy.
Gandolfi
Remo
R
Sarzi-Amadè
Mirko
M
Rastelli
Augusto
A