D.A. Evans Olefin Epoxidation via Peracids: An Introduction Chem 206 ■ The General Reaction Per-arachidonic acid epoxidation HOMO LUMO note labeled oxygen is transfered IC-C o*0-0 0-0 bond energy: -35 kcal/mol I Reaction rates are governed by olefin nucleophilicity. The rates of epoxidation of the indicated olefin relative to cyclohexene are provided 005 04 a The indicated olefin in each of the diolefinic substrates may be oxidized Me ■ The transition state E.J. Corey,JACS101.1586(1979) For a more detailed study see P Beak, JACS 113, 6281(1991) View from below olefin For theoretical studies of ts see R. D. Bach. JACS 1991. 113 2338 R. D. Bach, J. Org. Chem 2000, 65, 6715R O OH O + ● R R R R ● + ● R ● R R R O R OH OH OAc OH H Me Me Me Me O O H Me Me O H O Me Me Me Me Me O-O bond energy: ~35 kcal/mol View from below olefin ■ The transition state: 1.0 0.6 0.05 0.4 ■ The indicated olefin in each of the diolefinic substrates may be oxidized selectively. ■ Reaction rates are governed by olefin nucleophilicity. The rates of epoxidation of the indicated olefin relative to cyclohexene are provided below: HOMO pC–C Per-arachidonic acid Epoxidation E. J. Corey, JACS 101, 1586 (1979) ■ The General Reaction: D. A. Evans Olefin Epoxidation via Peracids: An Introduction Chem 206 LUMO s*O–O note labeled oxygen is transferfed For theoretical studies of TS see R. D. Bach, JACS 1991, 113, 2338 R. D. Bach, J. Org. Chem 2000, 65, 6715 For a more detailed study see P. Beak, JACS 113, 6281 (1991)