Electrochemical Dimerization of Phenylpropenoids and the Surprising Antioxidant Activity of the Resultant Quinone Methide Dimers. Issue 52 (26th November 2018)

• Record Type: Journal Article
• Authors: Romero, Kevin J.; Galliher, Matthew S.; Raycroft, Mark A. R.; Chauvin, Jean‐Philippe R.; Bosque, Irene; Pratt, Derek A.; Stephenson, Corey R. J.
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 52(2018)
• Page Start: 17125
• Page End: 17129
• Publication Date: 2018-11-26
• Subjects: antioxidants -- electrochemistry -- phenylpropenoids -- quinone methides -- resveratrol; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201810870
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A simple method for the dimerization of phenylpropenoid derivatives is reported. It leverages electrochemical oxidation of p ‐unsaturated phenols to access the dimeric materials in a biomimetic fashion. The mild nature of the transformation provides excellent functional group tolerance, resulting in a unified approach for the synthesis of a range of natural products and related analogues with excellent regiocontrol. The operational simplicity of the method allows for greater efficiency in the synthesis of complex natural products. Interestingly, the quinone methide dimer intermediates are potent radical‐trapping antioxidants; more so than the phenols from which they are derived—or transformed to—despite the fact that they do not possess a labile H‐atom for transfer to the peroxyl radicals that propagate autoxidation. Abstract : Quinone methide dimers are prepared via mild anodic oxidation mediated by a cheap and readily available amine base with excellent yield and regiocontrol. This strategy provides rapid access to intermediates for the synthesis of phenylpropenoid oligomers in a catalytic fashion, providing a new tool for the total synthesis of these complex molecules.