Two-component boronic acid catalysis for increased reactivity in challenging Friedel–Crafts alkylations with deactivated benzylic alcohols

Literature Information

Publication Date 2019-05-29
DOI 10.1039/C9OB01043B
Impact Factor 3.876
Authors

Hwee Ting Ang, Jason P. G. Rygus, Dennis G. Hall


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Abstract

A general and efficient boronic acid catalyzed Friedel–Crafts alkylation of arenes with benzylic alcohols was previously developed for the construction of unsymmetrical diarylmethane products (X. Mo, J. Yakiwchuk, J. Dansereau, J. A. McCubbin and D. G. Hall, J. Am. Chem. Soc., 2015, 137, 9694). Highly electron-deficient benzylic alcohols, however, were ineffective coupling partners due to the increased difficulty of C–O bond ionization. Herein, we report the use of perfluoropinacol as an effective co-catalyst to improve the reactivity of a boronic acid catalyst in the Friedel–Crafts benzylations of electronically deactivated primary and secondary benzylic alcohols. According to spectroscopic studies, it is believed that perfluoropinacol condenses with the arylboronic acid catalyst to form a highly electrophilic and Lewis acidic boronic ester. This in situ formed species enables a more facile ionization of the benzylic alcohols likely through a mode of activation promoted by a Lewis acid assisted hydronium Brønsted acid generated from the interactions of the transient boronic ester with hexafluoroisopropanol solvent and water.

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Organic & Biomolecular Chemistry

Organic & Biomolecular Chemistry
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Organic & Biomolecular Chemistry (OBC) publishes original and high impact research and reviews in organic chemistry. We welcome research that shows new or significantly improved protocols or methodologies in total synthesis, synthetic methodology or physical and theoretical organic chemistry as well as research that shows a significant advance in the organic chemistry or molecular design aspects of chemical biology, catalysis, supramolecular and macromolecular chemistry, theoretical chemistry, mechanism-oriented physical organic chemistry, medicinal chemistry or natural products. Articles published in the journal should report new work which makes a highly-significant impact in the field. Routine and incremental work is generally not suitable for publication in the journal. More details about key areas of our scope are below. In all cases authors should include in their article clear rationale for why their research has been carried out.

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