New catalytic alkylation of in situ generated perfluoro-alkyloxy-anions and perfluoro-carbanions

Galimberti, Maurizio; Fontana, Giovanni; Resnati, Giuseppe; Navarrini, W.

doi:10.1016/j.jfluchem.2005.09.005

Cited by 13 publications

(5 citation statements)

References 16 publications

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“…Normally,h eptafluoroisopropyl ethers were prepared through nucleophilic substitution reactions with the in situ generated heptafluoroisopropoxide anion from hexafluoroacetone and metal fluoride (Scheme 1a), [10] but the reaction was limited by the usage of the gaseous and highly toxic hexafluoroacetone.V ery recently,Ngai reported the synthesis of heptafluoroisopropyl aryl ethers through ap hotocatalytic heptafluoroisopropylation of N-aryl-N-hydroxylamides with ICF(CF 3 ) 2 followed by an intramolecular OCF(CF 3 ) 2 migration (Scheme 1b), [11] and Hu described one example of the heptafluoroisopropoxylation-bromination of the in situ generated aryne with BzOCF(CF 3 ) 2 prepared from hexafluoroacetone (Scheme 1c). [12] Obviously,t he substrate scope of these two synthetic methods was rather narrow.T herefore, the development of new reagents and reactions for the preparation of heptafluoroisopropyl ethers is of high demand.…”

Section: Introductionmentioning

confidence: 99%

Nucleophilic and Radical Heptafluoroisopropoxylation with Redox‐Active Reagents

Tong

Qing

2021

Angew Chem Int Ed

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The heptafluoroisopropyl group (CF(CF 3 ) 2 )i s prevalent in pharmaceuticals and agrichemicals.H owever, heptafluoroisopropoxylated (OCF(CF 3 ) 2 )c ompounds remain largely underexplored, presumably due to the lacko fefficient access to these compounds.H erein, we disclose the practical and efficient heptafluoroisopropoxylation reactions through the invention of aseries of redox-active N-OCF(CF 3 ) 2 reagents. These reagents were readily prepared from the oxidative heptafluoroisopropylation of hydroxylamines with AgCF-(CF 3 ) 2 .T he substitutions on the nitrogen atom significantly affected the properties and reactivities of N-OCF(CF 3 ) 2 reagents.A ccordingly,t wo types of N-OCF(CF 3 ) 2 reagents including N-OCF(CF 3 ) 2 phthalimide A and N-OCF(CF 3 ) 2 benzotriazolium salt O' ' were used as OCF(CF 3 ) 2 anion and radical precursors,r espectively.T his protocol enables the direct heptafluoroisopropoxylation of ar ange of substrates, delivering the corresponding products in moderate to excellent yields.

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Section: Introductionmentioning

confidence: 99%

Nucleophilic and Radical Heptafluoroisopropoxylation with Redox‐Active Reagents

Tong

Qing

2021

Angew Chem Int Ed

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“…On the other hand, tert ‐butyl fluorocarbonate (Boc−F) was verified as a tert ‐butyl source for the synthesis of tert ‐butyl esters of N ‐protected amino acids ( 184 ) in the presence of triethylamine and N , N ‐dimethylpyridin‐4‐amine (DMAP) (Scheme 30d) [53a] . Other alkyl fluoroformates were also confirmed as the excellent alkylation agents for the conversion of perfluoroacyl fluorides, perfluoroketones, and fluoroolefins to the respective hydrofluoroethers and hydrofluoroalkanes with KF or CsF (Scheme 30e) [53b] . Likewise, CH 3 O(CF 2 CF 2 O) n (CF 2 O) m CH 3 were synthesized from the reaction of perfluoropolyether diacyl fluorides with methyl fluoroformate in the presence of CsF using tetraglyme as a solvent [56] .…”

Section: Synthesis and Transformation Of Fluoroformates And Their Ana...mentioning

confidence: 96%

Recent Advances in the Synthesis and Transformation of Carbamoyl Fluorides, Fluoroformates, and Their Analogues

Liu

Zhang

2023

The Chemical Record

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Carbamoyl fluorides, fluoroformates, and their analogues are a class of important compounds and have been evidenced as versatile building blocks for the preparation of useful molecules in organic chemistry. While major achievements were made in the synthesis of carbamoyl fluorides, fluoroformates, and their analogues in the last half of 20th century, an increasing number of reports have focused on using O/S/Se=CF2 species or their equivalents as the fluorocarbonylation reagents for the direct construction of these compounds from the parent heteroatom‐nucleophiles in recent years. This review mainly summarizes the advances in the synthesis and typical application of carbamoyl fluorides, fluoroformates, and their analogues by the halide exchanges and fluorocarbonylation reactions since 1980.

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“…The following Table 3 summarizes all signals, acquired by 19 F, 1 H and 13 C NMR, related to product 2H-n 4 . Interestingly, it must be noted that the two different mono-hydrogen substituted groups, -CF 2 H and -CFH-, originate from the corresponding precursor that contains primary and secondary chlorine atoms.…”

Section: Nmrmentioning

confidence: 99%

“…Among them hydrofluoroethers (HFEs) became the subject of several studies [1][2][3]. They can be synthesized by different methods [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19].…”

Section: Introductionmentioning

confidence: 99%