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Enantioselective CpRu-Catalyzed Carroll Rearrangement. Metal Source Importance and Ligand Optimization

Published in European Journal of Organic Chemistry. 2008, no. 34, p. 5778-5785
Abstract The addition of unstabilized carbonyl nucleophiles to unsymmetrical allyl-metal fragments still represents a challenge to generate stereogenic centers enantio- and regioselectively. In this context, the decarboxylative Carroll rearrangement of allyl -keto esters is particularly interesting, since chiral,-unsaturated ketones are obtained. Herein, we show that CpRu half-sandwich complexes can, with selected enantiopure pyridine-monooxazoline ligands, catalyze this transformation and afford complete conversions along with good levels of regioselectivity and enantioselectivity. Even more challenging (electron-poor) substrates react (up to 86 % ee, branched/linear ratio 97:03). In addition, the use of an air-stable metal precursor, namely [CpRu(6-naphthalene)][PF6], allows the reaction to be carried out reproducibly evenin non-anhydrous THF with a catalyst loading as low as2 mol-%.
Keywords Allylic compoundsAir-stable precatalystC-C couplingN ligandsRutheniumEnantioselective catalysis
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LINDER, David et al. Enantioselective CpRu-Catalyzed Carroll Rearrangement. Metal Source Importance and Ligand Optimization. In: European Journal of Organic Chemistry, 2008, n° 34, p. 5778-5785. doi: 10.1002/ejoc.200800854 https://archive-ouverte.unige.ch/unige:7952

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Deposited on : 2010-06-21

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