Precise through-space control of an abiotic electrophilic aromatic substitution reaction

Kyle E. Murphy, Jessica L. Bocanegra, Xiaoxi Liu, H.-Y. Katharine Chau, Patrick C. Lee, Jianing Li and Severin T. Schneebeli ()
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Kyle E. Murphy: The University of Vermont
Jessica L. Bocanegra: The University of Vermont
Xiaoxi Liu: The University of Vermont
H.-Y. Katharine Chau: The University of Vermont
Patrick C. Lee: The University of Vermont
Jianing Li: The University of Vermont
Severin T. Schneebeli: The University of Vermont

Nature Communications, 2017, vol. 8, issue 1, 1-7

Abstract: Abstract Nature has evolved selective enzymes for the efficient biosynthesis of complex products. This exceptional ability stems from adapted enzymatic pockets, which geometrically constrain reactants and stabilize specific reactive intermediates by placing electron-donating/accepting residues nearby. Here we perform an abiotic electrophilic aromatic substitution reaction, which is directed precisely through space. Ester arms—positioned above the planes of aromatic rings—enable it to distinguish between nearly identical, neighbouring reactive positions. Quantum mechanical calculations show that, in two competing reaction pathways, both [C–H···O]–hydrogen bonding and electrophile preorganization by coordination to a carbonyl group likely play a role in controlling the reaction. These through-space-directed mechanisms are inspired by dimethylallyl tryptophan synthases, which direct biological electrophilic aromatic substitutions by preorganizing dimethylallyl cations and by stabilizing reactive intermediates with [C–H···N]–hydrogen bonding. Our results demonstrate how the third dimension above and underneath aromatic rings can be exploited to precisely control electrophilic aromatic substitutions.

Date: 2017
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DOI: 10.1038/ncomms14840

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