A Practical and Convenient Fluorination of 1,3-Dicarbonyl Compounds Using Aqueous HF in the Presence of Iodosylbenzene

Kitamura, Tsugio; Kuriki, Satoshi; Morshed, Mohammad Hasan; Hori, Yuichi

doi:10.1021/ol200632d

Cited by 61 publications

(27 citation statements)

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“…The reaction is fast, and the resulting bromides can be easily isolated and purified (Scheme 64). Kitamura et al [72] reported on the fluorination of diketones in the system PhIO-55% aq. HF-CH 2 Cl 2 at 40°C.…”

Section: Scheme 58mentioning

confidence: 99%

1,3-Diketones. Synthesis and properties

2015

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Section: Scheme 58mentioning

confidence: 99%

1,3-Diketones. Synthesis and properties

2015

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“…The concentration of the reaction mixture is also an important 80 factor in these fluorinations. When the concentration of the substrate was doubled from 0.12 M to 0.24 M, there was a dramatic improvement in the fluorination performed at 40 o C and the conversion to the monofluorinated product 12 increased from 54% (entry 7) to 89% (entry 9).…”

Section: This Journal Is © the Royal Society Of Chemistry [Year]mentioning

confidence: 99%

Electrophilic fluorination using a hypervalent iodine reagent derived from fluoride

et al. 2013

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The air and moisture stable fluoroiodane 8, readily prepared on a 6 g scale by nucleophilic fluorination of the hydroxyiodane 7 with TREAT-HF, has been used as an electrophilic fluorinating reagent for the first time to monofluorinate 1,3-ketoesters and difluorinate 1,3-diketones 10 in good isolated yields.In late 2011, Ritter reported the first electrophilic fluorination using the fluoride anion in a transfer fluorination between two palladium species. 1 An alternative, non-metal based strategy could be envisaged using cyclic hypervalent iodine(III) 15 compounds which have been shown to be mild, non-toxic and selective reagents for halogenation. Our research group is interested in designing new methods for introducing fluorine into organic molecules 5 because of the importance of incorporating fluorine into drug candidate 35 molecules. 6 Since Banks first reported SelectFluor in 1992, 7 the fluoraza reagents have become increasingly popular electrophilic fluorinating reagents because they are commercially-available, shelf-stable powders that can be used to fluorinate a wide variety of substrates. 8 The main disadvantage of these electrophilic 40 fluorinating reagents, however, is that they are very expensive because they are normally made from elemental fluorine. ____________________________________________________ Alternative reagents such as (difluoroiodo)arenes have been prepared from aqueous HF, but they are extremely moisture sensitive and are commonly used as a freshly prepared solution, without isolation, or they can be generated in situ. 9 Inspired by Togni's seminal work on electrophilic trifluoromethylation, 3 we 55 were interested in developing a new class of stable fluorinating reagents based on the cyclic hypervalent iodine(III) skeleton, but generated from cheap sources of fluoride. Here, we will report three different methods for the preparation of an air and moisture stable fluorinated hypervalent iodine reagent 8 and preliminary 60 results on its' fluorination of a series of 1,3-dicarbonyl substrates.Scheme 2 Synthesis of the fluoroiodane 8 using TREAT-HF

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“…Several commercial processes are available for various refrigerants , halon substitutes , and fluoromonomer . The applications of hydrofluoric acid (HF) is known for intramolecular Diels–Alder reactions and for fluorination of 1,3‐dicarbonyl compounds . However, there is no example of quinoxaline synthesis using aqueous HF (aq.…”

Section: Introductionmentioning

confidence: 99%