A Stereodynamic Redox-Interconversion Network of Vicinal Tertiary and Quaternary Carbon Stereocenters in Hydroquinone-Quinone Hybrid Dihydrobenzofurans

Angewandte Chemie
Golo StorchScott J Miller

Abstract

Reversible redox processes involving hydroquinones and quinones are ubiquitous in biological reaction networks, materials science, and catalysis. While extensively studied in intermolecular settings, less is known about intramolecular scenarios. Herein, we report hydroquinone-quinone hybrid molecules that form two-stereocenter dihydrobenzofurans via intramolecular cyclization under thermodynamic control. A π-methylhistidine peptide-catalyzed kinetic resolution allowed us to study the stereodynamic behavior of enantio- and diastereo-enriched dihydrofurans. In the course of this study, it was revealed that a reversible intramolecular redox-interconversion network connects all four possible stereoisomers via inversion of a quaternary carbon stereocenter without achiral intermediates. As a result, these findings on hydroquinone-quinone hybrid molecules provide insights into potential natural origin and synthetic access of the common dihydrobenzofuran motif.

References

Jan 13, 1967·Science·G W Kirby
Jul 2, 2003·European Journal of Medicinal Chemistry·Nikoletta J XanthopoulouPanos N Kourounakis
May 12, 2005·Chemical Reviews·Michael E Jung, Grazia Piizzi
Jul 19, 2005·Current Opinion in Biotechnology·Laurence B Davin, Norman G Lewis
Nov 14, 2008·Journal of the American Chemical Society·Chad A LewisScott J Miller
Jul 29, 2009·Angewandte Chemie·Jonathan ClaydenSteven R LaPlante
Apr 27, 2010·Journal of Asian Natural Products Research·Hong LiuHai-Sheng Chen
Sep 15, 2010·Angewandte Chemie·Jiří MíšekStefan Matile
Jan 31, 2012·The Journal of Organic Chemistry·Ximin LiVladimir B Birman
Jun 12, 2013·Journal of the American Chemical Society·Kyle D ReichlAlexander T Radosevich
Jun 13, 2013·Topics in Current Chemistry·Oliver Trapp
Jul 22, 2014·Angewandte Chemie·Hülya AldemirTobias A M Gulder
Feb 20, 2015·Chemical Reviews·Mårten WikströmGerhard Hummer
Nov 5, 2015·Angewandte Chemie·Alison E Wendlandt, Shannon S Stahl
Dec 15, 2016·Journal of the American Chemical Society·Mioy T HuynhSharon Hammes-Schiffer
Sep 22, 2017·Journal of the American Chemical Society·Byoungmoo KimScott J Miller

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Citations

Jun 8, 2019·Chemistry : a European Journal·Anthonius H J EngwerdaElias Vlieg
Apr 29, 2021·Chemical Communications : Chem Comm·Thomas Varlet, Géraldine Masson

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