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Issue 1, 2013
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Regio- and stereoretentive synthesis of branched, linear (E)- and (Z)-allyl fluorides from allyl carbonates under Ir-catalysis

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Abstract

This paper describes a new catalytic method for the regio- and stereocontrolled fluorination of allylic carbonates. This transformation uses TBAF·4tBuOH as the fluoride source and [Ir(COD)Cl]2 as the catalyst; the most commonly used [Ir(COD)Cl]2/phosphoramidite system is ineffective. Synthetically, this reaction is characterized by a high degree of structural conservation in going from substrates to the products. The fluorination of (E)-allylic carbonates leading to linear (E)-allylic fluorides (l : b > 20 : 1, E : Z > 20 : 1) is unprecedented and a unique feature of fluoride as the nucleophile. The first examples of transition metal catalyzed fluorination affording (Z)-allyl fluorides (Z : E ratio >20 : 1) are disclosed along with the successful fluorination of branched, linear (E)- and (Z)-allyl carbonates with [18F] fluoride in the presence of [Ir(COD)Cl]2. 18O-Labeling of the reactant reveals internal return during the allylic ionization step, and pathways for effective intra- and intermolecular isotope exchange.

Graphical abstract: Regio- and stereoretentive synthesis of branched, linear (E)- and (Z)-allyl fluorides from allyl carbonates under Ir-catalysis

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Publication details

The article was received on 19 Oct 2012, accepted on 23 Oct 2012 and first published on 24 Oct 2012


Article type: Edge Article
DOI: 10.1039/C2SC21789A
Citation: Chem. Sci., 2013,4, 89-96
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    Regio- and stereoretentive synthesis of branched, linear (E)- and (Z)-allyl fluorides from allyl carbonates under Ir-catalysis

    E. Benedetto, M. Tredwell, C. Hollingworth, T. Khotavivattana, J. M. Brown and V. Gouverneur, Chem. Sci., 2013, 4, 89
    DOI: 10.1039/C2SC21789A

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