title: Stereoselective umpolung tandem addition of heteroatoms to phenol.
abstract: Upon coordination to {TpW(PMe3)(NO)}, phenol tautomerizes to a cyclohexadienone (a 2H-phenol). The uncoordinated, nonaromatic double bond of this ligand undergoes stepwise addition of electrophiles followed by nucleophiles to produce 4,5-disubstituted cyclohexenone complexes. The metal stabilizes the intermediate cationic ligand and sterically blocks one face of the ligand, resulting in a high degree of stereo- and regiocontrol. These substituted cyclohexenones are readily liberated from the metal by oxidative decomplexation.
authors.affiliation: Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904, USA.
authors.forename: Michael A
authors.initials: MA
authors.lastname: Todd
authors.forename: Michal
authors.initials: M
authors.lastname: Sabat
authors.forename: William H
authors.initials: WH
authors.lastname: Myers
authors.forename: Timothy M
authors.initials: TM
authors.lastname: Smith
authors.forename: W Dean
authors.initials: WD
authors.lastname: Harman