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Synlett 2009(8): 1208-1218  
DOI: 10.1055/s-0028-1088126
ACCOUNT
© Georg Thieme Verlag Stuttgart ˙ New York

Intramolecular Anodic Olefin Coupling Reactions: Using Radical Cation Intermediates to Trigger New Umpolung Reactions

Kevin D. Moeller*
Department of Chemistry, Washington University, St. Louis, MO 63130, USA
Fax: +1(314)9354481; e-Mail: moeller@wustl.edu;
Further Information

Publication History

Received 24 September 2008
Publication Date:
08 April 2009 (online)

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Abstract

Anodic electrochemistry is a powerful tool for generating radical cation intermediates and initiating new cyclization reactions. Like most electrochemical reactions, the transformations involve umpolungs. In this review, recent studies examining the intramolecular coupling of radical cations derived from enol ethers, vinyl sulfides, and ketene acetals with carbon, oxygen, and nitrogen trapping groups are discussed to highlight their synthetic potential.

1 Introduction and Background

2 Arteannuins: A Backdrop for Discovery

3 A Detour: Ketene Acetals as Anodic Olefin Coupling Partners

4 Continuing the Detour: Ineleganolide and a Revised Working Model

5 Extending the Model: Nitrogen Trapping Groups

6 Back to Arteannuins: Completing the Ring Skeleton

7 Lactone Targets and a Couple of Final Points

8 Conclusions

Key words

electron transfer - radical cation intermediates - umpo­lung - cyclizations

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