Issue 31, 2022

Relative rates of alkylation for B-substituted triarylphosphines: an ortho-Boron group enhances reactivity on phosphorus

Abstract

Advancements in main-group catalysis are contingent on our ability to quantify effects that enhance reactivity in these systems. Herein we report the rates of alkylation for several substituted phosphines. We report that by incorporating a single pinacol boronic ester group in the ortho-position on triphenylphosphine, the rate of substitution with benzyl bromide is approximately 4.7 times faster than the parent compound as measured by initial rates. The corresponding meta- and para-isomers are only 1.3 and 1.5 times as fast, respectively. Using X-ray crystallographic data and quantum chemical calculations, we propose this rate acceleration occurs from an O to P electrostatic interaction that stabilizes the transition state.

Graphical abstract: Relative rates of alkylation for B-substituted triarylphosphines: an ortho-Boron group enhances reactivity on phosphorus

  • This article is part of the themed collection: New Talent

Supplementary files

Article information

Article type
Communication
Submitted
15 Mar 2022
Accepted
17 May 2022
First published
27 May 2022

Org. Biomol. Chem., 2022,20, 6183-6187

Author version available

Relative rates of alkylation for B-substituted triarylphosphines: an ortho-Boron group enhances reactivity on phosphorus

J. P. Mancinelli, S. Liu and S. M. Wilkerson-Hill, Org. Biomol. Chem., 2022, 20, 6183 DOI: 10.1039/D2OB00505K

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