Directing Electrophilic Aromatic Substitution Reactions from Above and Underneath Aromatic Rings
Severin T. Schneebeli, Ph.D.
The University of Vermont
Host: John MacDonald, Ph.D.
Ortho-, meta-, and para-directing groups have been used for decades to control the selectivities of electrophilic aromatic substitution (SEAr) reactions. Enzymes, on the other hand, are able to control this class of reactions efficiently by positioning protein residues above and underneath aromatic substrates. Inspired by the enzymatic approach, this presentation will discuss how abiotic SEAr reactions can be controlled1 precisely with partially flexible ester arms, placed over specific positions on aromatic systems. We are able to access new chiral materials2 with this bioinspired, through-space-directed approach, which are now being used as catalysts to build, replicate, and translate polymers.
(1) K. E. Murphy, J. L. Bocanegra, X. Liu, H.-Y. K. Chau, P. C. Lee, J. Li, S. T. Schneebeli. “Precise Through Space Control of an Abiotic Electrophilic Aromatic Substitution Reaction” Nature Commun. 2017, 8, 14840.
(2) X. Liu, Z. J. Weinert, M. Sharafi, C. Liao, J. Li, S. T. Schneebeli. “Regulating Molecular Recognition with C-Shaped Strips Attained by Chirality-Assisted Synthesis” Angew. Chem. Int. Ed. 2015, 54, 12772–12776.