title: Molybdenum(II)-Catalyzed Allylation of Electron-Rich Aromatics and Heteroaromatics.
abstract: The stable, readily available molybdenum(II) complexes [Mo(CO)(4)Br(2)](2) (B) and Mo(CO)(3)(MeCN)(2)(SnCl(3))Cl (C) have been found to catalyze C-C bond-forming allylic substitution with electron-rich aromatics (e.g., 15 + PhOMe --> 62) and heteroaromatics (e.g., 15 + 36 --> 88) as nucleophiles under mild conditions (room temperature, 30 min-3 h). Remarkable is the para-selectivity for anisole, whereas phenol tends to favor ortho-substitution in certain instances. Mechanistic and stereochemical experiments are indicative of Lewis-acid catalysis rather than a metal template-controlled process.
authors.affiliation: Department of Chemistry, University of Leicester, Leicester LE1 7RH, U.K., and Receptor Chemistry Unit, GlaxoWellcome PLC, Stevenage, Herts SG1 2NY, U.K.
authors.forename: Andrei V.
authors.initials: AV
authors.lastname: Malkov
authors.forename: Stuart L.
authors.initials: SL
authors.lastname: Davis
authors.forename: Ian R.
authors.initials: IR
authors.lastname: Baxendale
authors.forename: William L.
authors.initials: WL
authors.lastname: Mitchell
authors.forename: Pavel
authors.initials: P
authors.lastname: Kocovský