Syntheses and Applications of Monofluorinated Cyclopropanes

David, Emilie; Milanole, Gaëlle; Ivashkin, Pavel; Couve‐Bonnaire, Samuel; Jubault, Philippe; Pannecoucke, Xavier

doi:10.1002/chem.201202831

Cited by 71 publications

(29 citation statements)

References 105 publications

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“…Based on this strategy, the same authors later reported Johnson−Corey−Chaykovsky fluorocyclopropanation using sulfonium reagent 1a 19a with vinyl sulfones or vinyl sulfonamides to access synthetically challenging monofluorocyclopropanes 29 , which previously have been obtained generally via fluorocarbene and fluorocarbenoid chemistry. 16 The best conditions (Scheme the trans product was 0.9 kcal/mol lower in energy than for the corresponding cis-product.…”

Section: Accepted Manuscriptmentioning

confidence: 99%

“…Based on this strategy, the Veliks group then reported the Johnson-Corey-Chaykovsky fluorocyclopropanation using sulfonium reagent 1a 19a with vinyl sulfones or vinyl sulfonamides to access synthetically challenging monofluorocyclopropanes, 29 which were previously generally obtained via fluorocarbene and fluorocarbenoid chemistry. 16 The best conditions (Scheme 12), which involved sodium hydride as base and THF as an appropriate solvent, exhibited broad scope of functionalized aryl, heteroaryl, and cyclohexyl vinyl sulfones 63 to give fluorocyclopropanes 64a-f with good yields of the major trans-product.…”

Section: Scheme 11 Fluoromethylene Transfer To Aldehydes and Ketones; Isolated Yields Are Given With Nmr Yields In Parenthesesmentioning

confidence: 99%

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Synthetic Applications of Monofluoromethylsulfonium Salts

Melngaile¹,

Veliks²

2021

Synthesis

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Monofluoromethylsulfonium salts are emerging reagents for the fluoromethylation and fluoromethylenation or fluorometyhlene transfer. This type of reagents display simple approach for introduction of fluoromethyl group into wide range of nucleophiles upon mild basic conditions. Recently, fluoromethylsulfonium salts have been demonstrated to act as a synthetic equivalent of otherwise challenging fluoromethylene synthon. For instance, these reagents can be used for the direct synthesis of monofluoroepoxides and fluorocyclopropanes from activated alkenes via sulfur fluoromethylide intermediate. Sulfonium salts are an alternative, easy-to-handle option to volatile and environmentally concerning freons for achieving monofluorinated compounds. This review focuses on synthetic application of these reagents known to date.

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Section: Accepted Manuscriptmentioning

confidence: 99%

Section: Scheme 11 Fluoromethylene Transfer To Aldehydes and Ketones; Isolated Yields Are Given With Nmr Yields In Parenthesesmentioning

confidence: 99%

Synthetic Applications of Monofluoromethylsulfonium Salts

Melngaile¹,

Veliks²

2021

Synthesis

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“…6,9,38 The first report on the synthesis of gem-difluorocyclopropane was published in 1970 by Sargeant. The efficacy of drugs containing fluorine is found to be high due to enhanced activity, bioavailability and retarded drug metabolism.…”

Section: Synthesis Of Gem-difluorocyclopropanesmentioning

confidence: 99%

Recent advances in the syntheses, transformations and applications of 1,1-dihalocyclopropanes

et al. 2015

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gem-Dihalocyclopropanes have wide-spread applications in organic synthesis due to their versatile chemistry. They can serve as substrates for a large range of useful materials such as natural products, alkaloids, cyclopropanes, heterocycles, aromatic ring systems etc. Normally the dihalocyclopropanes are prepared by the addition of dihalocarbene to alkene, but due to the great synthetic efficacy of gem-dihalocyclopropanes a number of methods have been developed for their synthesis. Generally gem-dihalocyclopropanes exist as strained cyclic systems with astonishing kinetic stability. They are capable of undergoing transformations leading to a variety of products which have potential applications in various synthetic organic chemistry fields.

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“…Fluorinated cyclopropanes have become extraordinary structural motifs which attracted much attention in organic synthesis, drug discovery and agrochemistry over the last years . In particular, highly potent compounds bearing a gem ‐difluorocyclopropyl substituent were disclosed in recent patents, e.g.…”

Section: Introductionmentioning

confidence: 99%

N‐Difluorocyclopropyl‐Substituted Pyrazoles: Synthesis and Reactivity

et al. 2019

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Difluorocyclopropanation of N‐vinylazoles with the CF3SiMe3–NaI system was studied. It was found that N‐vinylpyrazoles could be transformed into the corresponding N‐difluorocyclopropyl‐substituted derivatives. The method was efficient on a 100 g scale and could be applied for the preparation of various functionalized regioisomeric pyrazole derivatives bearing a gem‐difluorocyclopropane moiety, such as amines, carboxylic acids, aldehydes, bromides, and boronic esters. It was found that N‐difluorocyclopropylpyrazole moiety tolerated many common reagents including nitrating mixture, bromine, aqueous acids and alkali, KMnO4, LiBH4, and Pd0 complexes; it was unstable towards AlCl3, catalytic hydrogenation and lithiation conditions. The products obtained are advanced building blocks which of potential importance to medicinal and agrochemistry.

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Syntheses and Applications of Monofluorinated Cyclopropanes

Cited by 71 publications

References 105 publications

Synthetic Applications of Monofluoromethylsulfonium Salts

Synthetic Applications of Monofluoromethylsulfonium Salts

Recent advances in the syntheses, transformations and applications of 1,1-dihalocyclopropanes

N‐Difluorocyclopropyl‐Substituted Pyrazoles: Synthesis and Reactivity

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