Efficient S<sub>N</sub>2 Fluorination of Primary and Secondary Alkyl Bromides by Copper(I) Fluoride Complexes

Yan-pin, Liu; Chen, Chaohuang; Li, Huaifeng; Huang, Kuo‐Wei; Tan, Jianwei; Weng, Zhiqiang

doi:10.1021/om4008967

Cited by 49 publications

(30 citation statements)

References 64 publications

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“…Recently, Weng and co-workers have reported the synthesis of a cationic Cu I bifluoride salt (28), ligated by a phenantroline-derived ligand [100]. This compound was prepared in 92% yield by reacting Cu(O …”

Section: Other Transition Metal Bifluoridesmentioning

confidence: 99%

Transition metal bifluorides

Nahra

Brill

Gómez‐Herrera

et al. 2016

Coordination Chemistry Reviews

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A c c e p t e d M a n u s c r i p t HighlightsSince their discovery four decades ago, transition metal bifluoride complexes have long been considered as unwanted byproducts, a necessary evil, on the route to access fluoride complexes. Until recently, reports on this chemistry almost always presented these complexes as a fluke discovery. However, with the recent increase in reports and applications involving such species, a renewed interest in these complexes has been observed. Most of the work done in this area, so far, has been directed toward the synthesis and quite challenging characterization of these complexes, yet mostly neglecting the behavior of such species and their influence on catalytic processes. The aim of this work is to present a summary of the various preparation methods, characterization techniques and applications of reported transition metal bifluoride complexes. It is our hope that by centralizing all information available on such species, future efforts aimed at exploiting the full potential of transition metal bifluoride species can be facilitated.

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Section: Other Transition Metal Bifluoridesmentioning

confidence: 99%

Transition metal bifluorides

Nahra

Brill

Gómez‐Herrera

et al. 2016

Coordination Chemistry Reviews

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“…Considering the low solubility of KF in organic solvents, [23] and the initial finding that [IPrCuF] can be formed from KF and [IPrCuOTf], we speculated that the fluorination reaction involves the formation of [IPrCuF] from [IPrCuOTf] and KF, followed by the fluorination of alkyl triflate by the [IPrCuF] (Scheme 1). [17] According to this proposal, the copper catalyst functions as a phase-transfer catalyst which provides a soluble and nucleophilic source of fluoride from the rather insoluble KF. Considering that we have already demonstrated the feasibility of the formation of [IPrCuF] under the reaction conditions [Equation (2)] we explored its reactivity in the presence of alkyl triflates.…”

Section: Methodsmentioning

confidence: 99%

Mild Copper‐Catalyzed Fluorination of Alkyl Triflates with Potassium Fluoride

2014

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A chemoselective catalytic fluorination of alkyl triflates is described using potassium fluoride as a fluoride source. Excellent yields of the desired alkyl fluorides are obtained after one hour at 45 °C using 2 mol% of the copper catalyst. With 10 mol% of the catalyst, full conversion can be achieved in less than 10 minutes at 45 °C, and thus makes this procedure potentially suited for the preparation of (18) F-labeled PET probes. As a result of the mild reaction conditions, only the substitution products are observed with no evidence of common side reactions, such as elimination. Reported is a preliminary study of the reaction scope, which demonstrates that the fluorination can be performed in the presence of a wide range of functional groups. Evidence suggests an unusual role of the [IPrCuOTf] catalyst as a phase-transfer catalyst and points to [IPrCuF] as the active fluorinating reagent (IPr=1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene).

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“…One problem is that in most cases fluorination of alkyl electrophiles with metal fluorides occurs only at high temperature and usually leads to the formation of a significant amount of elimination products. For example, a significant amount of elimination products has recently been observed in reactions of alkyl electrophiles with a copper fluoride diamino complex, performed for over 15 h at 110 °C in MeCN 17. The second problem is that the formation of metal fluoride complexes is difficult to accomplish under catalytic conditions.…”

Section: Development Of the Catalytic Fluorination Reactionmentioning

confidence: 99%

Mild Copper‐Catalyzed Fluorination of Alkyl Triflates with Potassium Fluoride

2014

View full text Add to dashboard Cite

A chemoselective catalytic fluorination of alkyl triflates is described using potassium fluoride as a fluoride source. Excellent yields of the desired alkyl fluorides are obtained after one hour at 45 °C using 2 mol % of the copper catalyst. With 10 mol % of the catalyst, full conversion can be achieved in less than 10 minutes at 45 °C, and thus makes this procedure potentially suited for the preparation of 18F‐labeled PET probes. As a result of the mild reaction conditions, only the substitution products are observed with no evidence of common side reactions, such as elimination. Reported is a preliminary study of the reaction scope, which demonstrates that the fluorination can be performed in the presence of a wide range of functional groups. Evidence suggests an unusual role of the [IPrCuOTf] catalyst as a phase‐transfer catalyst and points to [IPrCuF] as the active fluorinating reagent (IPr=1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene).

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Efficient S_N2 Fluorination of Primary and Secondary Alkyl Bromides by Copper(I) Fluoride Complexes

Cited by 49 publications

References 64 publications

Transition metal bifluorides

Transition metal bifluorides

Mild Copper‐Catalyzed Fluorination of Alkyl Triflates with Potassium Fluoride

Mild Copper‐Catalyzed Fluorination of Alkyl Triflates with Potassium Fluoride

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Efficient SN2 Fluorination of Primary and Secondary Alkyl Bromides by Copper(I) Fluoride Complexes

Cited by 49 publications

References 64 publications

Transition metal bifluorides

Transition metal bifluorides

Mild Copper‐Catalyzed Fluorination of Alkyl Triflates with Potassium Fluoride

Mild Copper‐Catalyzed Fluorination of Alkyl Triflates with Potassium Fluoride

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Efficient S_N2 Fluorination of Primary and Secondary Alkyl Bromides by Copper(I) Fluoride Complexes