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Tandem Oxidative Nucleophilic Hydrogen Substitution/B-O Cyclization Enables Chiral Near-Infrared N,O,B-Chelated
Hua Wang1, Yuting Zhang1, Wenxin Gu1
1The Key Laboratory of Functional Molecular Solids of Ministry of Education, College of Chemistry and Molecular Sciences, Anhui Normal University, Wuhu241002, China.
Abstract:
We report a mild, modular tandem strategy that transforms readily available B-substituted BODIPYs into a new class of N,O,B-chelated BODIPYs with intense near-infrared absorption/emission. The key transformation involves oxidative nucleophilic substitution of α-hydrogens (ONSH) followed by intramolecular B-O cyclization, operating with diverse ketones (acetophenones, indanones, tetralones, acenaphthenone). X-ray crystallography reveals a tetrahedral boron center that is inherently stereogenic. Chiral resolution by HPLC and circular dichroism spectroscopy confirm the optical activity of the enantiomers.
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