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Synthesis 2020; 52(23): 3667-3674
DOI: 10.1055/s-0040-1706421
DOI: 10.1055/s-0040-1706421
paper
Asymmetric Synthesis of a Bicyclo[4.3.0]nonene Derivative Bearing a Quaternary Carbon Stereocenter: Desymmetrization of σ-Symmetrical Diketones through Intramolecular Addition of an Alkenyl Anion
This research was supported by the Japan Society for the Promotion of Science (JSPS), Grants-in-Aid for Scientific Research (KAKENHI) (Grant No. JP17K08208).
Further Information
Publication History
Received: 26 June 2020
Accepted after revision: 25 July 2020
Publication Date:
20 August 2020 (online)
Abstract
The enantioselective synthesis of a bicyclo[4.3.0]nonene derivative bearing a quaternary carbon stereocenter is achieved by employing a desymmetrization strategy involving an intramolecular addition. The intramolecular nucleophilic addition of a highly reactive carbanion generated from an alkenyl iodide in the presence of a chiral ligand occurs with discrimination of two keto carbonyl groups to give the corresponding bicyclic compound in 81% yield and 39% ee. Asymmetric synthesis via an intramolecular desymmetrization strategy using a chiral ligand–carbanion complex represents a complementary approach to using chiral organocatalysts or chiral ligand–transition-metal complexes.
Key words
desymmetrization - asymmetric synthesis - alkenyl lithium - quaternary carbon stereocenter - bicyclo[4.3.0]noneneSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0040-1706421.
- Supporting Information
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Enantioselective syntheses through desymmetrization via intermolecular reactions of carbanion species are reported, see: