Regioselective and Enantiospecific Rhodium-Catalyzed Allylic Alkylation Reactions Using Copper(I) Enolates: Synthesis of (−)-Sugiresinol Dimethyl Ether
- 1 July 2003
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 125 (30), 8974-8975
- https://doi.org/10.1021/ja035983p
Abstract
The transition metal-catalyzed allylic alkylation represents a fundamentally important cross-coupling reaction for the construction of ternary carbon stereogenic centers. We have developed a regioselective and enantiospecific rhodium-catalyzed allylic alkylation of acyclic unsymmetrical allylic alcohol derivatives using copper(I) enolates to prepare β-substituted ketones. This protocol represents a convenient asymmetric Claisen rearrangement surrogate in which α-substituted enolates permit the introduction of an additional stereogenic center. The synthetic utility of this transformation was highlighted in the construction of a trans-1,2-disubstituted cyclohexene and the total synthesis of (−)-sugiresinol dimethyl ether. Finally, we anticipate that copper(I) enolates may prove useful nucleophiles in related metal-catalyzed reactions.Keywords
This publication has 13 references indexed in Scilit:
- Regio- and Enantiospecific Rhodium-Catalyzed Arylation of Unsymmetrical Fluorinated Acyclic Allylic Carbonates: Inversion of Absolute ConfigurationJournal of the American Chemical Society, 2003
- Regio- and Enantiospecific Rhodium-Catalyzed Allylic Etherification Reactions Using Copper(I) Alkoxides: Influence of the Copper Halide Salt on SelectivityJournal of the American Chemical Society, 2002
- Regio- and Diastereoselective Tandem Rhodium-Catalyzed Allylic Alkylation/Pauson−Khand Annulation ReactionsJournal of the American Chemical Society, 2001
- 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
- Regiodefined Apparent Hydroallylation toward α,β-Unsaturated Carbonyl Compounds Attained by the Rhodium-Catalyzed One-Pot ProcedureJournal of the American Chemical Society, 2000
- Regioselective and Enantiospecific Rhodium-Catalyzed Intermolecular Allylic Etherification with Ortho-Substituted PhenolsJournal of the American Chemical Society, 2000
- Palladium-Catalyzed Allylic Alkylations without Isomerization—Dream or Reality?Angewandte Chemie International Edition, 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
- Palladium-Catalyzed Asymmetric Alkylation of Ketone EnolatesJournal 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