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Published on: June 21, 2017
Aryl carbonyls and carbinols as proelectrophiles for Friedel-Crafts benzylation and alkylation
P Veeraraghavan Ramachandran1, Randy Lin1, Abdulkhaliq A Alawaed1
1Department of Chemistry, Herbert C. Brown Center for Borane Research, Purdue University West Lafayette Indiana 47907 USA chandran@purdue.edu.
Abstract:
Friedel-Crafts benzylation/alkylation using benzylic, tertiary, and homobenzylic alcohols; aryl aldehydes, aryl ketones, and the highly challenging aryl carboxylic acids and esters as proelectrophiles has been achieved using borane-ammonia and TiCl4, greatly broadening the scope of useable substrates. Incorporation of deactivated aromatic proelectrophiles and specificity for substitution at the benzylic position are demonstrated in the synthesis of various di- and triarylalkane products. Dual protocols allow for the use of standard nucleophilic solvents (benzene, toluene, etc.) or for stoichiometric addition of more valuable nucleophiles including furans, thiophenes, and benzodioxoles.
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