Sodium dispersion-mediated reductive dimerization of benzylic halides for symmetrical bibenzyls: Column-free applications to natural products

We report a method for the synthesis of symmetrical bibenzyls by the reductive dimerization of benzylic halides using sodium dispersion (SD). SD, a reagent consisting of sodium particles dispersed in mineral oil, has recently attracted attention as a safer but more reactive source of sodium than sod...

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Bibliographic Details
Main Authors: Bubwoong Kang, Tatsuro Imamura, Tetsuya Satoh
Format: Article
Language:English
Published: Elsevier 2024-12-01
Series:Tetrahedron Green Chem
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Online Access:http://www.sciencedirect.com/science/article/pii/S2773223124000177
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Summary:We report a method for the synthesis of symmetrical bibenzyls by the reductive dimerization of benzylic halides using sodium dispersion (SD). SD, a reagent consisting of sodium particles dispersed in mineral oil, has recently attracted attention as a safer but more reactive source of sodium than sodium lump. We have found that the reductive dimerization of benzylic halides proceeds within 1 h at room temperature in tetrahydrofuran (THF) solvent using SD as a reducing agent. This method is highly sustainable for the synthesis of symmetrical bibenzyls since it uses sodium, which is abundant on earth. As the SD-derived mineral oil in the crude product can be readily removed, three natural products were synthesized on a gram scale without the need for column chromatography. The utility of this reaction was also exemplified by a decagram-scale reaction using 2-methyltetrahydrofuran, known as a green alternative solvent to THF.
ISSN:2773-2231