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

Benedetto, Elena, Tredwell, Matthew, Hollingworth, Charlotte, Khotavivattana, Tanatorn, Brown, John M. and Gouverneur, Veronique 2013. Regio- and stereoretentive synthesis of branched, linear (E)- and (Z)-allyl fluorides from allyl carbonates under Ir-catalysis. Chem. Sci. 4 (1) , pp. 89-96. 10.1039/c2sc21789a

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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.

Item Type: Article
Status: Published
Schools: Medicine
Last Modified: 12 Jun 2019 11:15
URI: http://orca.cf.ac.uk/id/eprint/122199

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