Issue 35, 2018

Enantioselective fluorination of homoallylic alcohols enabled by the tuning of non-covalent interactions

Abstract

The study of the enantioselective fluorination of homoallylic alcohols via chiral anion phase transfer (CAPT) catalysis using an in situ generated directing group is described. Multivariate correlation analysis, including designer π-interaction derived parameters, revealed key structural features affecting the selectivity at the transition state (TS). Interpretation of the parameters found in the model equation highlights the key differences as well as similarities for the reaction of homoallylic and allylic substrates. A similar T-shaped π-interaction was found to occur between the substrate and the catalyst. The tuning of this crucial interaction by identification of the best combination of phosphoric acid catalyst and boronic acid directing group allowed for the development of a methodology to access γ-fluoroalkenols in typically high enantioselectivities (up to 96% ee).

Graphical abstract: Enantioselective fluorination of homoallylic alcohols enabled by the tuning of non-covalent interactions

Supplementary files

Article information

Article type
Edge Article
Submitted
20 may 2018
Accepted
25 iyl 2018
First published
03 avq 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2018,9, 7153-7158

Enantioselective fluorination of homoallylic alcohols enabled by the tuning of non-covalent interactions

J. A. S. Coelho, A. Matsumoto, M. Orlandi, M. J. Hilton, M. S. Sigman and F. D. Toste, Chem. Sci., 2018, 9, 7153 DOI: 10.1039/C8SC02223B

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