Advertisement
No access
Perspective
Chemistry

Efficient Fluorination of Organic Molecules with Chiral Anions

An efficient and flexible method for adding rings bearing fluorine atoms can help improve the biological activity and materials properties of organic molecules.
Science
23 Dec 2011
Vol 334, Issue 6063
pp. 1651-1652

Abstract

Many pharmaceuticals and agrochemicals, as well as liquid-crystal materials, contain fluorine atoms. The introduction of the small, highly electronegative fluorine atom into an organic molecule can greatly change its physical and biological properties and, with careful design, improve its chemical and metabolic stability as well as its biological activity (1). In many cases, fluorine has been introduced on an aromatic ring or as a trifluoromethyl group, but fluorine substitution at a chiral carbon center—one that has right- or left-handed stereochemistry—is attracting increasing attention, because adding a fluorine atom to a chiral center can alter the conformation of the molecule and allow fine-tuning of its biological activities. On page 1681 of this issue, Rauniyar et al. (2) report on an efficient fluorocyclization reaction that converts achiral compounds containing double bonds into complex, chiral fluorine derivatives. A chiral anionic phase-transfer catalyst helps a normally insoluble reagent enter the organic phase and selectively add fluorine to a carbon atom.

Get full access to this article

View all available purchase options and get full access to this article.

References

1
Ojima I., Ed., Fluorine in Medicinal Chemistry and Chemical Biology (Wiley-Blackwell, Chichester, UK, 2009).
2
Rauniyar V., Lackner A. D., Hamilton G. L., Toste F. D., Science 334, 1681 (2011).
3
Hintermann L., Togni A., Angew. Chem. Int. Ed. 39, 4359 (2000).
4
Hamashima Y., Yagi K., Takano H., Tamás L., Sodeoka M., J. Am. Chem. Soc. 124, 14530 (2002).
5
Paull D. H., Scerba M. T., Alden-Danforth E., Widger L. R., Lectka T., J. Am. Chem. Soc. 130, 17260 (2008).
6
Ma J.-A., Cahard D., Chem. Rev. 108, PR1 (2008).
7
Lectard S., Hamashima Y., Sodeoka M., Adv. Synth. Catal. 352, 2708 (2010).
8
Marigo M., Fielenbach D., Braunton A., Kjærsgaard A., Jørgensen K. A., Angew. Chem. Int. Ed. 44, 3703 (2005).
9
Steiner D. D., Mase N., Barbas C. F., Angew. Chem. Int. Ed. 44, 3706 (2005).
10
Benson T. D., MacMillan D. W. C., J. Am. Chem. Soc. 127, 8826 (2005).
11
Ishimaru T., et al.., Angew. Chem. Int. Ed. 47, 4157 (2008).
12
Kim D. Y., Park E. J., Org. Lett. 4, 545 (2002).
13
Wang X., Lan Q., Shirakawa S., Maruoka K., Chem. Commun. (Camb.) 46, 321 (2010).
14
Lazano O., et al.., Angew. Chem. Int. Ed. 50, 8105 (2011).
15
Lacour J., Moraleda D., Chem. Commun. (Camb.) 2009, 7073 (2009).

(0)eLetters

eLetters is an online forum for ongoing peer review. Submission of eLetters are open to all. eLetters are not edited, proofread, or indexed. Please read our Terms of Service before submitting your own eLetter.

Log In to Submit a Response

No eLetters have been published for this article yet.

Information & Authors

Information

Published In

Science
Volume 334 | Issue 6063
23 December 2011

Submission history

Published in print: 23 December 2011

Permissions

Request permissions for this article.

Authors

Affiliations

Mikiko Sodeoka
Synthetic Organic Chemistry, RIKEN, and ERATO, JST, 2-1 Hirosawa, Wako, Saitama 351-0198 JAPAN.

Notes

Metrics & Citations

Metrics

Article Usage
Altmetrics

Citations

Export citation

Select the format you want to export the citation of this publication.

Cited by

  1. Verification of interfacial monolayer conformation of weakly hydrophilic diamide derivatives possessing a fluorocarbon-sandwiched hydrocarbon, Colloids and Surfaces A: Physicochemical and Engineering Aspects, 606, (125389), (2020).https://doi.org/10.1016/j.colsurfa.2020.125389
    Crossref
  2. Trifluoromethyl aldimines: an overview in the last ten years, Tetrahedron, 72, 30, (4449-4489), (2016).https://doi.org/10.1016/j.tet.2016.06.015
    Crossref
  3. Stereoselective α-Fluorination of N -Acyloxazolidinones at Room Temperature within 1 h , The Journal of Organic Chemistry, 79, 13, (6206-6220), (2014).https://doi.org/10.1021/jo500957d
    Crossref
  4. Chiral organic contact ion pairs in metal-free catalytic enantioselective oxidative cross-dehydrogenative coupling of tertiary amines to ketones, Chemical Science, 4, 6, (2645), (2013).https://doi.org/10.1039/c3sc50604e
    Crossref
  5. New insights on reaction pathway selectivity promoted by crown ether phase-transfer catalysis: Model ab initio calculations of nucleophilic fluorination, Journal of Molecular Catalysis A: Chemical, 363-364, (489-494), (2012).https://doi.org/10.1016/j.molcata.2012.07.030
    Crossref
Loading...

View Options

Check Access

Log in to view the full text

AAAS ID LOGIN

AAAS login provides access to Science for AAAS Members, and access to other journals in the Science family to users who have purchased individual subscriptions.

Log in via OpenAthens.
Log in via Shibboleth.

More options

Purchase access to this article

Download and print this article within 24 hours for your personal scholarly, research, and educational use.

View options

PDF format

Download this article as a PDF file

Download PDF

Full Text

FULL TEXT

Media

Figures

Multimedia

Tables

Share

Share

Share article link

Share on social media