Recent Advances and Perspectives of Transition Metal‐Catalyzed Asymmetric Fluorination Reactions

Chen, Chaohuang; Fu, Liang; Chen, Pinhong; Liu, Guosheng

doi:10.1002/cjoc.201700489

Cited by 40 publications

(11 citation statements)

References 70 publications

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“…[137,138] Additionally, the presence of fluorine atom can change pK a values as well as bring conformational changes due to gauche effect. [139][140][141][142][143][144][145][146][147] Significantly, on the basis of transfer of fluorine atom, three significant synthetic approaches i. e. nucleophilic fluorination, electrophilic fluorination and radical fluorination can be utilized to incorporate fluorine atom into organic molecules for the generation of carbon-fluorine bond. Detailed progression of synthetic methodology in the field of organofluorination has been discussed in several reviews within past few years.…”

Section: Synthetic Methodologies For Directed Cà H Bond Fluorination ...mentioning

confidence: 99%

Recent Advances in First‐Row Transition‐Metal‐Mediated C−H Halogenation of (Hetero)arenes and Alkanes

et al. 2022

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The ubiquity of carbon halogen bonds in the structural core of numerous biomolecules and pharmaceuticals along with their role as synthetic precursors in various organic reactions makes the organic halides a crucial class of organic compounds. Consequently, the synthesis of organic halides with high regioselectivity is of paramount importance in synthetic chemistry. In nature, selective halogenation is achieved by metalloenzymes with high efficiency involving high-valent iron-oxo as active species. The high selectivity of halogenating enzymes attracted considerable attention leading to the development of several biomimetic approaches for CÀ H halogenation. Moreover, the emergence of transition metal (TM) catalyzed site-selective CÀ H halogenation protocols through the development of several directed strategies has also been impressive. There has been significant development in the first row TM catalyzed CÀ H halogenation reactions despite the dominance of late transition metals catalysts in this field. But in literature, there is no up-to-date recent review article that consolidates bio-mimetic as well as synthetic strategies of CÀ H halogenation (X = Cl, Br, I) containing organo-fluorination with all the first-row transition metals. Thus, we got motivated and have focused to elucidate the recent developments of first row TM-catalyzed CÀ H halogenation of (hetero)arenes and alkanes through biomimetic approaches as well as directed and undirected strategies in this present review. Additionally, this review covers the recent progresses in the CÀ H fluorination methodologies. Altogether, the review will provide a combined overview of all the strategies of first-row transition-metalmediated CÀ H halogenation reactions that may benefit the scientific community towards the development of new methodologies in this field.

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Section: Synthetic Methodologies For Directed Cà H Bond Fluorination ...mentioning

confidence: 99%

Recent Advances in First‐Row Transition‐Metal‐Mediated C−H Halogenation of (Hetero)arenes and Alkanes

et al. 2022

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“…[1][2][3][4] Nucleophilic [5][6][7][8][9] and electrophilic [10][11][12][13][14] fluorinations provide the general approaches to organofluorides. [15][16][17][18] Arenes and alkenes are common nucleophiles, and their electrophilic fluorination has been considered as a reliable strategy for the generation of organofluorides. Compared with the reactive and corrosive F 2 , 19 trifluoromethyl hypofluorite (CF 3 OF), hypofluorous acid (HOF), cesium fluoroxysulfate (CsSO 4 F), and xenon difluoride (XeF 2 ), 20 reagents bearing N-F bonds, [21][22][23][24][25] including Selectfluor [23][24] and NFSI, 25 are relatively stable and operable readily (Figure 1a).…”

Section: Introductionmentioning

confidence: 99%

“…Inscrutably, the reaction did not work in EtNO 2, nPrNO 2, or PhNO 2 , possibly, due to the poor solubility of Selectfluor in these solvents (entries[13][14][15]. Brønsted acid or Lewis acid additives failed to facilitate this transformation (entries[16][17][18]. While basic additives such as KH 2 PO 4 , Na 3 PO 4 , and Na 2 CO 3 were favorable for the conversion (entries[19][20][21][22], achieving an 82% yield of 2a using 0.4 equiv of Na 2 CO 3 as the additive (entry 22).…”

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confidence: 99%

Nitromethane-Enabled Fluorination of Styrenes and Arenes

et al. 2020

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The electrophilic fluorination of unsaturated compounds provides a reliable approach to the generation of organofluorides, which are used widely in agrochemicals, pharmaceuticals, and other materials. Numerous active electrophilic fluorine reagents, such as the fluorine molecule (F 2 ) or xenon difluoride (XeF 2 ), have been applied in fluorination. However, these reagents suffer from their hazardous, toxic, corrosive, and poor selective properties, and the relatively weak electrophilicity of Selectfluor or N-fluorobenzenesulfonimide (NFSI) usually limits their broad applications. Herein, we disclose nitromethane (MeNO 2 ) as an efficient activator of Selectfluor and NFSI, as well as a stabilizer of carbocations.Therefore, the fluoro-azidation, fluoroamination, fluoroesterification of styrenes, and C-H fluorination of (hetero)arenes were well realized just by the facilitation of MeNO 2 . The mild reaction conditions and practicability made our current method a versatile protocol for accessing organofluorides.

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“…Nevertheless, while some complex polyfunctional fluorine-containing molecules possessing useful properties represent the ultimate target of synthetic chemistry, more fundamental research still focuses on the formation of the C-F bond. In this regard, electrophilic fluorination is one of the most pioneering and rapidly developing areas of study [61][62][63][64][65][66][67]. Conceptually, this approach requires a carbon-centered nucleophile and an electrophilic source of fluorine.…”

Section: Introductionmentioning

confidence: 99%

Kitamura Electrophilic Fluorination Using HF as a Source of Fluorine

et al. 2020

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This review article focused on the innovative procedure for electrophilic fluorination using HF and in situ generation of the required electrophilic species derived from hypervalent iodine compounds. The areas of synthetic application of this approach include fluorination of 1,3-dicarbonyl compounds, aryl-alkyl ketones, styrene derivatives, α,β-unsaturated ketones and alcohols, homoallyl amine and homoallyl alcohol derivatives, 3-butenoic acids and alkynes.

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Recent Advances and Perspectives of Transition Metal‐Catalyzed Asymmetric Fluorination Reactions

Cited by 40 publications

References 70 publications

Recent Advances in First‐Row Transition‐Metal‐Mediated C−H Halogenation of (Hetero)arenes and Alkanes

Recent Advances in First‐Row Transition‐Metal‐Mediated C−H Halogenation of (Hetero)arenes and Alkanes

Nitromethane-Enabled Fluorination of Styrenes and Arenes

Kitamura Electrophilic Fluorination Using HF as a Source of Fluorine

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