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Scientific article
English

Enantio- and Regioselective CpRu Catalyzed Carroll Rearrangement

Published inPure and applied chemistry, vol. 80, no. 5, p. 967-977
Publication date2008
Abstract

The addition of unstabilized carbonyl nucleophiles to allyl-metal fragments still represents a challenge for generating stereoselectively tertiary (and quaternary) stereogenic centers. In this context, the decarboxylative Carroll rearrangement of secondary and tertiary allyl β-ketoesters is particularly interesting since chiral γ,δ-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 rearrangements of allylic β-ketoesters performed with these zwitterionic species occur with better regio- and enantioselectivity.

Keywords
  • Allyl complexes
  • Enantioselective catalysis
  • Hexacoordinated phosphorus
  • N ligands
  • Ruthenium
Note14th International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS-14). - Nara (Japan). - 2–6 August 2007
Citation (ISO format)
AUSTERI, Martina et al. Enantio- and Regioselective CpRu Catalyzed Carroll Rearrangement. In: Pure and applied chemistry, 2008, vol. 80, n° 5, p. 967–977. doi: 10.1351/pac200880050967
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