Journal
PURE AND APPLIED CHEMISTRY
Volume 80, Issue 5, Pages 967-977Publisher
WALTER DE GRUYTER GMBH
DOI: 10.1351/pac200880050967
Keywords
allyl complexes; enantioselective catalysis; ruthenium; N ligands; hexacoordinated phosphorus
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The addition of unstabilized carbonyl nucleophiles to allyl-metal fragments still represents a challenge for generating stereo selectively tertiary (and quaternary) stereogenic centers. In this context, the decarboxylative Carroll rearrangement of secondary and tertiary allyl beta-ketoesters is particularly interesting since chiral gamma,delta-unsaturated ketones are obtained. Herein, we show that CpRu half-sandwich complexes can, in the presence of selected enantiopure diimine ligands, catalyze this transformation and afford complete conversions and decent level of enantiomeric excess. Zwitterionic adducts of a hexacoordinated phosphorus anion and CpRu moieties were also associated and shown to generate air-, moisture-, and microwave-stable catalysts that can be readily purified and recycled. Carroll re-arrangements of allylic beta-ketoesters performed with these zwitterionic species occur with better regio- and enantioselectivity.
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