New synthetic approaches toward OCF<sub>3</sub>-containing compounds

Hao, Bo‐Ya; Han, Yong-Jun; Zhang, Yuecheng; Liang, Yong‐Min

doi:10.1039/d3ob00258f

Cited by 14 publications

(2 citation statements)

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“…The trifluoromethoxy (OCF 3 ) group has emerged as a valuable functional group in various fields of chemical research. [82,83] Notably, the OCF 3 group in aryl trifluoromethylethers, unlike its methoxy analogue (OCH 3 ), lies orthogonal to the arene ring due to the poor conjugation of the oxygen lone pair in the aromatic ring owing to its delocalization in the adjacent CÀ F bond. [84][85][86] Traditionally, aryl trifluoromethylethers were obtained by electrophilic trifluoromethylation of phenols.…”

Section: O-centered Radicals 21 Trifluoromethoxylation (Ocf 3 )mentioning

confidence: 99%

Review and Theoretical Analysis of Fluorinated Radicals in Direct C_Ar−H Functionalization of (Hetero)arenes

Fernandes,

Giri,

Houk

et al. 2024

Angewandte Chemie

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We highlight key contributions in the field of direct radical CAr–H (hetero)aromatic functionalization involving fluorinated radicals. A compilation of Functional Group Transfer Reagents and their diverse activation mechanisms leading to the release of radicals are discussed. The substrate scope for each radical is analyzed and classified into three categories according to the electronic properties of the substrates. Density functional theory computational analysis provides insights into the chemical reactivity of several fluorinated radicals through their electrophilicity and nucleophilicity parameters. Theoretical analysis of their reduction potentials also highlights the remarkable correlation between electrophilicity and oxidizing ability. It is also established that highly fluorinated radicals (e.g.•OCF3) are capable of engaging in single‐electron transfer (SET) processes rather than radical addition, which is in good agreement with experimental literature data. A reactivity scale, based on activation barrier of addition of these radicals to benzene is also elaborated using the high accuracy DLPNO‐(U)CCSD(T) method.

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Section: O-centered Radicals 21 Trifluoromethoxylation (Ocf 3 )mentioning

confidence: 99%

Review and Theoretical Analysis of Fluorinated Radicals in Direct C_Ar−H Functionalization of (Hetero)arenes

Fernandes,

Giri,

Houk

et al. 2024

Angewandte Chemie

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“…Alkali metal alkoxides are recognized as key reagents in organic synthesis, especially for nucleophilic alkoxylation reactions that establish carbon–oxygen (C–O) bonds and produce ethers. 1 Recent breakthroughs have thrusted this area into new territories, especially in the synthesis of trifluoromethyl ethers (R-OCF 3 ), 2 promising exciting developments in agrochemicals and pharmaceuticals. 3 Traditionally, the production of alkali metal trifluoromethoxides [M][OCF 3 ] requires fluorophosgene (carbonyl fluoride, F 2 C O) and alkali metal fluorides (M–F, Fig.…”

Section: Introductionmentioning

confidence: 99%

Halo-perfluoroalkoxylation of gem-difluoroalkenes with short-lived alkali metal perfluoroalkoxides in triglyme

Kawai,

Kato,

Araki

et al. 2024

Chem. Sci.

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Catalyst‐Free Trifluoromethoxylation of Silyl Enol Ethers and Allyl Silanes with Bis(trifluoromethyl)peroxide

Maas,

Fasting,

Voßnacker

et al. 2024

Angewandte Chemie

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Radical trifluoromethoxylation is an attractive approach to prepare compounds featuring the important OCF3 group, however most existing methods have focused on aromatic substrates. Here, we report novel methodologies with alkenyl substrates employing bis(trifluoromethyl)peroxide (BTMP) as a practical and comparatively atom economical trifluoromethoxylating reagent. With silyl enol ether substrates, switching reaction solvent allows for the synthesis of either α‐(trifluoromethoxy)ketone products or unprecedented alkenyl‐OCF3 species. Furthermore, allyl silanes have been employed as substrates for the first time, affording allyl(trifluoromethyl)ether products in good yields. In each case, the methods operate at room temperature without large excesses of the alkene substrate while, in contrast to previous radical trifluoromethoxylation reactions, no catalyst, light or other activators are required.

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New synthetic approaches toward OCF₃-containing compounds

Abstract: Fluorinated organic compounds stand as an important class of organic molecules and play a key role in both academic and industrial communities due to the unique nature of fluorine. Among...

Cited by 14 publications

References 105 publications

Review and Theoretical Analysis of Fluorinated Radicals in Direct C_Ar−H Functionalization of (Hetero)arenes

Review and Theoretical Analysis of Fluorinated Radicals in Direct C_Ar−H Functionalization of (Hetero)arenes

Halo-perfluoroalkoxylation of gem-difluoroalkenes with short-lived alkali metal perfluoroalkoxides in triglyme

Catalyst‐Free Trifluoromethoxylation of Silyl Enol Ethers and Allyl Silanes with Bis(trifluoromethyl)peroxide

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New synthetic approaches toward OCF3-containing compounds

Abstract: Fluorinated organic compounds stand as an important class of organic molecules and play a key role in both academic and industrial communities due to the unique nature of fluorine. Among...

Cited by 14 publications

References 105 publications

Review and Theoretical Analysis of Fluorinated Radicals in Direct CAr−H Functionalization of (Hetero)arenes

Review and Theoretical Analysis of Fluorinated Radicals in Direct CAr−H Functionalization of (Hetero)arenes

Halo-perfluoroalkoxylation of gem-difluoroalkenes with short-lived alkali metal perfluoroalkoxides in triglyme

Catalyst‐Free Trifluoromethoxylation of Silyl Enol Ethers and Allyl Silanes with Bis(trifluoromethyl)peroxide

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Product

Resources

About

New synthetic approaches toward OCF₃-containing compounds

Review and Theoretical Analysis of Fluorinated Radicals in Direct C_Ar−H Functionalization of (Hetero)arenes

Review and Theoretical Analysis of Fluorinated Radicals in Direct C_Ar−H Functionalization of (Hetero)arenes