Bis(cyclopentadienyliron)arene Complexes: A new route to the synthesis and functionalization of polyaromatic ethers

Article abstract of DOI:10.1021/om00013a055

A new development in the chemistry of arenes activated toward S_NAr reactions by the cyclopentadienyliron (FeCp⁺) moiety is presented in this work. A class of diiron complexes of diphenoxybenzenes was prepared in a highly efficient and very mild fashion. Dihydroxy aromatic compounds served as dinucleophiles, allowing for the formation of the diiron complexes. This could be achieved in either a one or two step procedure. A wide variety of dinucleophiles were incorporated into this study, as well as a number of FeCp⁺ activated arenes. It is shown that these reactions are not inhibited by bulky substituents on either the dinucleophiles or activated arenes. The diiron complexes themselves could also undergo S_NAr reactions, provided that the complexed arenes contained a chlorine substituent. This allowed for the functionalization of the complexes with species that could not be introduced directly in their syntheses. The carbon nucleophiles generated from ethyl cyanoacetate or (phenylsulfonyl)acetonitrile could be attached to the complexed ethers in this manner. The FeCp⁺ moieties were removed easily by photolytic demetalation which allowed for the recovery of a wide range of functionalized diphenoxybenzenes. This methodology is advantageous over all those previously reported and should be a practical route to the synthesis of aromatic ethers.