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Updated: Oct 3, 2026

Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Molybdenum(II)-Catalyzed Allylation of Electron-Rich Aromatics and Heteroaromatics
Andrei V. Malkov1, Stuart L. Davis, Ian R. Baxendale
1Department of Chemistry, University of Leicester, Leicester LE1 7RH, U.K., and Receptor Chemistry Unit, GlaxoWellcome PLC, Stevenage, Herts SG1 2NY, U.K.
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.
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