Asymmetric Hydroxylation, Epoxidation and Sulfoxidation Catalyzed by Vaulted Binaphthyl Metalloporphyrins

Article abstract of DOI:10.1021/jo00298a046

A chiral, vaulted binaphthyl porphyrin (1) has been prepared from 5α,10β,15α,20β-tetrakis(o-aminophenyl)porphyrin and (R)-(+)-2,2'-dimethoxy-1,1'-bi-6-naphthoyl chloride in 79 percent yield.Asymmetric oxygenations of alkanes, alkenes, and alkyl sulfides were catalyzed with the chloroiron(III) and chloromanganese(III) complexes of 1 with good yields and high stereoselectivities.The first catalytic asymmetric hydroxylations are reported for 1-Fe(III)Cl with enantiomeric excesses in the range of 40-72 percent.The corresponding manganese catalyst, 1-Mn(III)Cl, gave much lower enantiomeric excesses.For catalytic asymmetric epoxidations, enantiomeric excesses were in the range of 20-72 percent.Prochiral alkyl sulfides gave sulfoxides with 14-48 percent ee with 1-Fe(III)Cl.