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- Title
Photocatalytic Reductive Radical‐Polar Crossover for a Base‐Free Corey–Seebach Reaction.
- Authors
Donabauer, Karsten; Murugesan, Kathiravan; Rozman, Urša; Crespi, Stefano; König, Burkhard
- Abstract
A metal‐free generation of carbanion nucleophiles is of prime importance in organic synthesis. Herein we report a photocatalytic approach to the Corey–Seebach reaction. The presented method operates under mild redox‐neutral and base‐free conditions giving the desired product with high functional group tolerance. The reaction is enabled by the combination of photo‐ and hydrogen atom transfer (HAT) catalysis. This catalytic merger allows a C−H to carbanion activation by the abstraction of a hydrogen atom followed by radical reduction. The generated nucleophilic intermediate is then capable of adding to carbonyl electrophiles. The obtained dithiane can be easily converted to the valuable α‐hydroxy carbonyl in a subsequent step. The proposed reaction mechanism is supported by emission quenching, radical–radical homocoupling and deuterium labeling studies as well as by calculated redox‐potentials and bond strengths.
- Subjects
ABSTRACTION reactions; CARBANIONS; ORGANIC synthesis; CATALYSIS; BOND strengths
- Publication
Chemistry - A European Journal, 2020, Vol 26, Issue 57, p12945
- ISSN
0947-6539
- Publication type
Academic Journal
- DOI
10.1002/chem.202003000