166. Regio- and Enantioselective Allylation of Phenols via Decarboxylative Allylic Etherification of Allyl Aryl Carbonates Catalyzed by (Cyclopentadienyl)ruthenium(II) Complexes and Pyridine-Hydrazone Ligands
     Léo Egger, Cecilia Tortoreto, Thierry Achard, David Monge, Abel Ros, Rosario Fernández, José M. Lassaletta, Jérôme Lacour
     Adv. Synth. Catal. 2015, 357, 3325-3331

(Cyclopentadienyl)tris(acetonitrile)ruthenium hexafluorophosphate [CpRu(CH₃CN)₃][PF₆] in combination with pyridine-hydrazone ligands efficiently catalyzes the asymmetric decarboxylative allylic rearrangement of allyl aryl carbonates. Formations of C–O bonds with high regio- and enantioselectivity ratios (up to 95:5 and 98% ee) are obtained. Good stereocontrol of the pseudotetrahedral geometry of the CpRu moiety is achieved by the hydrazone ligand and its “electron-poor” nature is evidenced through the epimerization of hexacoordinated TRISPHAT-N anion.

DOI: 10.1002/adsc.201500534 

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