Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2021 Jan 6;19(1):162-165.
doi: 10.1039/d0ob02152k.

Enantiospecific deoxyfluorination of cyclic α-OH-β-ketoesters

Christopher Mairhofer  1 , Victoria Haider, Thomas Bögl, Mario Waser
Affiliations

Enantiospecific deoxyfluorination of cyclic α-OH-β-ketoesters

Christopher Mairhofer et al. Org Biomol Chem. .

Abstract

We herein report the deoxyfluorination of cyclic α-hydroxy-β-ketoesters using diethylaminosulfur trifluoride (DAST). The reaction proceeds with excellent levels of stereospecificity, giving the configurationally inverted α-fluoro-β-ketoesters in high yields under operationally simple conditions.

PubMed Disclaimer

Conflict of interest statement

Conflicts of interest

There are no conflicts to declare.

Figures

Scheme 1
Scheme 1
Our previously developed α-hydroxylation and α-fluorination of β-ketoesters 4 and the herein investigated deoxyfluorination of alcohols 2 to access α-F-β-ketoesters 3.
Scheme 2
Scheme 2
Application scope employing the conditions shown in Table 1, entry 6 (all reactions were run using 0.05–0.1 mmol 2) and the proposed stereospecific inversion mechanism.
See this image and copyright information in PMC

References

    1. For selected reviews on nucleophilic fluorination methods covering deoxyfluorinations as well: Hollingworth C, Gouverneur V. Chem Commun. 2012;48:2929–2942. Liang T, Neumann CN, Ritter T. Angew Chem Int Ed. 2013;52:8214–8264. Wu J. Tetrahedron Lett. 2014;55:4289–4294. Champagne PA, Desroches J, Hamel JD, Vandamme M, Paquin JF. Chem Rev. 2015;115:9073–9174. Ni C, Hu M, Hu J. Chem Rev. 2015;115:765–825. Yerien DE, Bonesi S, Postigo A. Org Biomol Chem. 2016;14:8398–8427. Dykstra KD, Ichiishi N, Krska SW, Richardson PF. Fluorine in Life Sciences: Pharmaceuticals, Medicinal Diagnostics, and Agrochemicals. Academic Press; 2019. pp. 1–90.

    1. For reviews on deoxyfluorinations: Al-Maharik N, O’Hagan D. Aldrichimica Acta. 2011;44:65–75. Hu W-L, Hu X-G, Hunter L. Synthesis. 2017:4917–4930.

    1. Middleton WJ. J Org Chem. 1975;40:574–578.
    1. Singh RP, Shreeve JM. Synthesis. 2002:2561–2578.
    1. Baptista L, Bauerfeldt GF, Arbilla G, Silva EC. J Mol Struct. 2006;761:73–81.

Publication types

LinkOut - more resources