Ag(I) and Pd(II)-Catalyzed Friedel-Crafts-Type Allylic SubstitutionPhenol Derivatives

摘要

The C-terminus of cyanide is known to strongly interact with some transition metal speciesto afford the stable metal cyanides.In the presence of excess amounts of cyanide,thecorresponding cyanometallates are reversibly formed.Recently,we achieved allylicisocyanation catalyzed by Pd(II) species,using allylic phosphate as an electrophile.1 The atecomplexes (Me3Si)[Pd(CN)3] and/or (Me3Si)2[Pd(CN)4] were generated in situ fromPd(OAc)2 and trimethylsilyl cyanide (TMSCN),and those served as both Lewis acidactivating allylic phosphate and C-blocked cyanide reagents.We hypothesized that anotherallylic substitution occurred with the combination of transition metal catalyst andstoichiometric TMSCN when a stronger nucleophile than [Pd(CN)3]-was employedtogether.