Leveraging the Persistent Radical Effect in the Synthesis of trans‐2,3‐Diaryl Dihydrobenzofurans

A simple method for accessing trans‐2,3‐diaryl dihydrobenzofurans is reported. This approach leverages the equilibrium between quinone methide dimers and their persistent radicals. This equilibrium is disrupted by phenols that yield comparatively transient phenoxyl radicals, leading to cross‐couplin...

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Published inAngewandte Chemie International Edition Vol. 62; no. 34; pp. e202305801 - n/a
Main Authors Roldan, Bec J., Hammerstad, Travis A., Galliher, Matthew S., Keylor, Mitchell H., Pratt, Derek A., Stephenson, Corey R. J.
Format Journal Article
LanguageEnglish
Published WEINHEIM Wiley 21.08.2023
Wiley Subscription Services, Inc
EditionInternational ed. in English
Subjects
Antioxidants
Biomimetics
Chemistry
Chemistry, Multidisciplinary
Cross coupling
Dihydrobenzofuran
Functional groups
Natural products
Phenols
Physical Sciences
Quinone Methides
Quinones
Radicals
Resveratrol
Science & Technology
Synthesis
ASYMMETRIC-SYNTHESIS
NATURAL-PRODUCTS
ARYLATION
Dihydrobenzofuran
Quinone Methides
DIMERS
Radicals
4-HYDROXYSTILBENES
Antioxidants
KINETICS
Resveratrol
HOPEAHAINOL
CHEMISTRY
ATOMS
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Summary:A simple method for accessing trans‐2,3‐diaryl dihydrobenzofurans is reported. This approach leverages the equilibrium between quinone methide dimers and their persistent radicals. This equilibrium is disrupted by phenols that yield comparatively transient phenoxyl radicals, leading to cross‐coupling between the persistent and transient radicals. The resultant quinone methides with pendant phenols rapidly cyclize to form dihydrobenzofurans (DHBs). This putative biomimetic access to dihydrobenzofurans provides superb functional group tolerance and a unified approach for the synthesis of resveratrol‐based natural products. A simple, diastereoselective protocol for accessing trans‐2,3‐diaryl dihydrobenzofurans through efficient cross‐coupling of persistent quinone radicals, derived from quinone methide dimers, and transient phenoxyl radicals is described. DFT calculations have provided insight into the reaction pathway. This transformation offers access to a wide variety of dihydrobenzofuran‐containing natural products.
Bibliography:https://doi.org/10.26434/chemrxiv‐2022‐2bmrf
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A previous version of this manuscript has been deposited on a preprint server
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ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.202305801