Regio- and Enantiospecific Rhodium-Catalyzed Arylation of Unsymmetrical Fluorinated Acyclic Allylic Carbonates: Inversion of Absolute Configuration
- 23 May 2003
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 125 (24) , 7158-7159
- https://doi.org/10.1021/ja035216q
Abstract
The transition metal-catalyzed allylic substitution with unstabilized carbon nucleophiles represents an important cross-coupling reaction for the construction of ternary carbon stereogenic centers. We have developed a new regio- and enantiospecific rhodium-catalyzed allylic alkylation of acyclic unsymmetrical chiral nonracemic allylic alcohol derivatives with aryl zinc bromides. This study demonstrates that the hydrotris(pyrazolyl)borate rhodium catalyst and zinc(II) halide salt are crucial for efficiency, while the addition of lithium bromide to the catalyst is necessary for obtaining optimal regiospecificity. The stereochemical course of this reaction was established through the synthesis of (S)-ibuprofen, which demonstrated that the alkylation proceeds with net inversion of absolute configuration consistent with direct addition of the nucleophile to the metal center followed by reductive elimination.Keywords
This publication has 19 references indexed in Scilit:
- The Crystallographic Structure of a Lewis Acid-Assisted Chiral Brønsted Acid as an Enantioselective Protonation Reagent for Silyl Enol EthersJournal of the American Chemical Society, 2002
- Regioselective Rhodium-Catalyzed Allylic Linchpin Cross-Coupling Reactions: Diastereospecific Construction of anti-1,3-Carbon Stereogenic Centers and C2-Symmetrical FragmentsJournal of the American Chemical Society, 2001
- Asymmetric Carbon–Carbon Bond‐Forming Reactions: Asymmetric Allylic Alkylation ReactionsPublished by Wiley ,2000
- Regioselective and Enantiospecific Rhodium-Catalyzed Intermolecular Allylic Etherification with Ortho-Substituted PhenolsJournal of the American Chemical Society, 2000
- Enantiospecific Synthesis of Allylamines via the Regioselective Rhodium-Catalyzed Allylic Amination Reaction [J. Am. Chem. Soc. 1999, 121, 6761−6762].Journal of the American Chemical Society, 1999
- Conservation of Absolute Configuration in the Acyclic Rhodium-Catalyzed Allylic Alkylation Reaction: Evidence for an Enyl (σ + π) Organorhodium IntermediateJournal of the American Chemical Society, 1998
- Palladium-catalyzed coupling of allylic acetates with aryl- and vinylstannanesThe Journal of Organic Chemistry, 1990
- Enantioselective homogeneous catalysis involving transition-metal-allyl intermediatesChemical Reviews, 1989
- Stereo- and regiochemistry in palladium-catalyzed nucleophilic substitution of optically active (E)- and (Z)-allyl acetatesThe Journal of Organic Chemistry, 1986
- A greatly improved procedure for ruthenium tetroxide catalyzed oxidations of organic compoundsThe Journal of Organic Chemistry, 1981