1,2-Bis-perfluoroalkylations of alkenes and alkynes with perfluorocarboxylic anhydrides<i>via</i>the formation of perfluoroalkylcopper intermediates

Tagami, Takuma; Aoki, Yuji; Kawamura, Shintaro; Sodeoka, Mikiko

doi:10.1039/d1ob01529j

Cited by 9 publications

(10 citation statements)

References 60 publications

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“…In 2021, Sodeoka and colleagues reported the first bisperfluoroalkylation of alkynes (and alkenes) toward the construction of bisperfluoroalkylated alkenes (and alkanes). In this work, a mixture of perfluoroalkyl carboxylic anhydrides, urea/H 2 O 2 , and [Cu(CH 3 CN) 4 ]PF 6 as the catalyst in the presence of the alkyne (or alkene) afforded the respective bisperfluoroalkylated alkenes (or 1,2-bisperfluoroalkylated alkanes from alkenes).…”

Section: Formation Of C(sp 2 )–Rf Bonds: Syntheses Of Perfluoroalkyl-...mentioning

confidence: 99%

“…Several perfluoroalkylation reagents have been developed to build perfluoroalkylated compounds for diverse applications in organic syntheses, materials sciences, and medicinal chemistry . For example, sodium perfluoroalkylsulfinates (R F SO 2 Na), perfluoroalkylsulfonyl chlorides (R F SO 2 Cl), S -(fluoroalkyl)diphenylsulfonium salts, perfluoroalkyl carboxylic acids, TMSC n F 2 n +1 , perfluoroacid anhydrides, − R F -hypervalent iodine reagents, and perfluoroalkyl halides R F X. , The latter, perfluoroalkyl halides (R F X), are more widely employed compared to other reagents due to their commercial availability, laboratory stability, and convenience in operation. Particularly, radical protocols employing perfluoroalkyl iodides R F –I as radical precursors have been extensively studied .…”

Section: Introductionmentioning

confidence: 99%

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Radical Perfluoroalkylation of Aliphatic Substrates

2023

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A selection of perfluoroalkylation reactions of aliphatic substrates that display methodological and synthetic amplitude will be studied, giving examples of their applications and mechanistic details. An array of synthetic approaches for fluoroalkylation reactions are documented; in particular, radical protocols are prominent among perfluoroalkylation methods. To that effect, addition reactions of perfluoroalkyl radicals R F (R F =C n F 2n+1 , n > 1) to unsaturated organic substrates serve as one of the most direct and efficacious ways to access fluoroalkylated scaffolds. The syntheses of perfluoroalkyl-substituted vinyl, alkynyl, and allylic compounds; the syntheses of perfluoroalkyl-substituted hydro-, iodo-, and oxy-perfluoroalkylated alkanes and olefins; the syntheses of perfluoroalkyl-substituted carbonyl compounds; the syntheses of perfluoroalkyl-substituted enamides, amides, thioamides, and hydrazones; and multicomponent perfluoroalkylation reactions will be studied. While there are a number of accomplished reports on organofluorination, we aim to provide an overview of radical-involved perfluoroalkylation reactions of aliphatic substrates, covering examples from 2018 to early 2023, as summarized in Tables 1−4.

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Section: Formation Of C(sp 2 )–Rf Bonds: Syntheses Of Perfluoroalkyl-...mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Radical Perfluoroalkylation of Aliphatic Substrates

2023

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“…Last year, the copper-mediated synthesis of diverse bisperfluoroalkylated derivatives from alkenes with perfluorcarboxylic anhydrides has been published by Sodeoka [48] et al The method was extended for the double functionalization of alkynes as well providing the appropriate tetrasubstituted alkenes in acceptable yields (Scheme 45). Mechanistic investigations revealed that the bistrifluormethylation reaction proceeds via the formation of a vinyl radical, in a similar manner as proposed previously by Cook.…”

Section: Alkyne Functionalizationmentioning

confidence: 99%

“…In the last year, Sodeoka [48] realized the copper‐mediated synthesis of diverse bisperfluoroalkylated derivatives in moderate to good yields in the reaction of alkenes with perfluorocarboxylic anhydrides in the presence of H 2 O 2 (Scheme 40). Mechanistic investigations revealed that the key step in this reaction is the formation of a stable perfluoroalkylcopper intermediate achieved with the aid of a bipyridyl ligand.…”

Section: Alkyltrifluoromethylation Reactionsmentioning

confidence: 99%

Carbotrifluoromethylations of C−C Multiple Bonds (Excluding Aryl‐ and Alkynyltrifluoromethylations)

Aradi

Kiss

2023

Chemistry A European J

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Organofluorine chemistry has become an expanding area of research in organic chemistry and drug design. The synthesis of fluorine-containing molecules has received high significance in synthetic chemistry. Trifluoromethylative difunctionalizations of carbon-carbon multiple bonds with the simultaneous introduction of a CF 3 group and another function have considerable relevance. Because of the high importance of carbon-carbon bond-forming reactions in organic synthesis, carbotrifluoromethylations are considered to be a field of synthetic chemistry of increasing importance. Our current goal in this review is to summarize recent developments of various trifluoromethylation reactions (excluding aryl-and alkynyl-trifluoromethylations) taking into consideration several main approaches, such as alkenyltrifluoromethylation, alkyltrifluoromethylation, carbonyltrifluoromethylation, and cyanotrifluoromethylation reactions.

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“…Finally, the reductive elimination of VI leads to the trisubstituted alkenes 4 – 42 and regenerates the Cu I L3 complex I for the next catalytic cycle. The high anti -stereoselectivity of the reaction is likely depending on the relative stability of the intermediate VI , where the sterically demanding alkyl group is anti to the large Ar′Cu III L3 group …”

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confidence: 99%

Copper-Catalyzed anti-Selective Radical 1,2-Alkylarylation of Terminal Alkynes

et al. 2022

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A copper-catalyzed highly anti-selective radical 1,2-alkylarylation of terminal alkynes with aryl boronic acids and alkyl bromides has been established. The reaction exhibits high compatibility with a wide range of terminal alkynes and diverse aryl boronic acids, thus providing facile access to various stereodefined trisubstituted alkenes in high yield under mild reaction conditions. Preliminary mechanistic investigations support the formation of alkyl radicals and their subsequent addition to alkynes in the reaction.

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1,2-Bis-perfluoroalkylations of alkenes and alkynes with perfluorocarboxylic anhydridesviathe formation of perfluoroalkylcopper intermediates

Abstract: 1,2-Bis-perfluoroalkylations of alkenes/alkynes with perfluorocarboxylic anhydrides.

Cited by 9 publications

References 60 publications

Radical Perfluoroalkylation of Aliphatic Substrates

Radical Perfluoroalkylation of Aliphatic Substrates

Carbotrifluoromethylations of C−C Multiple Bonds (Excluding Aryl‐ and Alkynyltrifluoromethylations)

Copper-Catalyzed anti-Selective Radical 1,2-Alkylarylation of Terminal Alkynes

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