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Enhanced Reactivity for Aromatic Bromination via Halogen Bonding with Lactic Acid Derivatives
Sarah I Baker1, Mahshid Yaghoubi1, Samantha L Bidwell1
1Department of Chemistry and Biochemistry, University of California, 5200 N. Lake Road, Merced, California 95343, United States.
Abstract:
We report a new method for regioselective aromatic bromination using lactic acid derivatives as halogen bond acceptors with N-bromosuccinimide (NBS). Several structural analogues of lactic acid affect the efficiency of aromatic brominations, presumably via Lewis acid/base halogen-bonding interactions. Rate comparisons of aromatic brominations demonstrate the reactivity enhancement available via catalytic additives capable of halogen bonding. Computational results demonstrate that Lewis basic additives interact with NBS to increase the electropositive character of bromine prior to electrophilic transfer. An optimized procedure using catalytic mandelic acid under aqueous conditions at room temperature was developed to promote aromatic bromination on a variety of arene substrates with complete regioselectivity.
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