Unfunctionalized olefins, epoxidation porphyrin complex

Epoxidation of olefins was catalyzed by the ruthenium(II) complex of the above perfluorinated y3-diketone in the presence of 2-methylpropanal (Scheme 50). Unfunctionalized olefins were epoxidized with a cobalt-containing porphyrin complex, and epoxidation of styrene derivatives was catalyzed by chiral salen manganese complexes (248) (Scheme 50). In the latter case, chemical yields were generally high, however, the products showed low enantiomeric excess with the exception of indene (92% ee). [Pd(C7Fi5COCHCOC7Fi5)2] efficiently catalyzed the oxidation of terminal olefins to methyl ketones with f-butylhydroperoxide as oxidant in a benzene-bromoperfluoro-octane solvent system (Scheme 50). In all these reactions, the product isolation and efficient catalyst recycle was achieved by a simple phase separation. 

Polymer RuCO-porphyrins 102 and 103 (Seheme 48) were used for the eyelopropanation reaetion of styrenes but they were also tested in the epoxidation reaetion. Contraiy to eyelopropanation for whieh moderate enantioselectivities and low aetivities were observed, these Ru porphyrin complexes gave good ee (up to 76%) and activity (up to 89%) for AE of unfunctionalized olefines [204], Recently, Simmoneaux showed that iron catalyst 326 derived from electropolymerized tetraspirofluorenyl porphyrin (Scheme 138) led to moderate yields without chiral induction [205],... 

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