Intramolecular construction of trifluoromethyl group by the palladium-catalyzed reaction of 2,3,3-trifluoroallylic carbonates with O -nucleophiles

Hoshino, Yuji; Isa, Kazuki; Hanakawa, Taisyun; Tsuji, Hiroaki; Kawatsura, Motoi

doi:10.1016/j.tet.2018.02.022

Cited by 3 publications

(2 citation statements)

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“…In these reactions, [Pd(C 3 H 5 )Cl] 2 and dppf served as a pre-catalytic system and AgBF 4 activated the system (Scheme 68). [55] A number of aliphatic alcohols and phenols participated in the reaction to produce a diverse array of trifluoromethyl substituted enol ethers.…”

Section: Synthesis Of Trifluoromethyl Derivativesmentioning

confidence: 99%

“…For example, O ‐based nucleophiles 240 coupled with 2,3,3‐trifluoroallylic carbonates 239 to afford trifluoromethyl vinyl ethers ( 241 ). In these reactions, [Pd(C 3 H 5 )Cl] 2 and dppf served as a pre‐catalytic system and AgBF 4 activated the system (Scheme ) . A number of aliphatic alcohols and phenols participated in the reaction to produce a diverse array of trifluoromethyl substituted enol ethers.…”

Section: Generation Of Trifluoromethanesmentioning

confidence: 99%

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Recent Advances in Transition Metal‐Catalyzed Functionalization of gem‐Difluoroalkenes

Koley

Altman

2020

Israel Journal of Chemistry

130

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gem-Difluorinated alkenes are readily accessible building blocks that can undergo functionalization to provide a broad spectrum of fluorinated and non-fluorinated products. Herein, we review recent (since 2017) transition metalcatalyzed transformations of these specialized alkenes and summarize general reactivity patterns of these reactions. Many transition metal-catalyzed reactions undergo net CÀ F bond functionalization reactions to deliver monofluorinated products. These reactions typically proceed through β-fluoroalkylmetal intermediates that readily eliminate a βfluoride to deliver monofluoroalkene products. A second series of reactions exploit coinage metal fluorides to add F À to the gem-difluorinated alkene, and further functionalization delivers trifluoromethyl-containing products. In stark contrast, few transition metal-catalyzed reactions proceed in net "fluorine-retentive processes" to deliver difluoromethylenebased products. Reactions Proceeding via β-Fluoride Eliminationgem-Difluoroalkenes react with a variety of transition metalbased catalyst systems (e. g. Cu, Co, Mn, Pd, Ni, Ru, Rh) in net CÀ F functionalization reactions. These reactions typically proceed through a β-fluoroalkylmetal intermediate that readily undergoes β-fluoride elimination to form a new alkene based product (Scheme 1). At first, reaction of a substrate-ligated complex (1) to the gem-difluoroalkene 2, proceeds through a four-membered transition state 3 to generate the intermediate 4. This process involves the matching of the anionic ligand (Y) with the cationic α,α-difluorinated position of the alkene, which generates an intermediate metalalkyl bearnig two βfluoride atoms. Subsequent β-fluoride elimination generates [a] S.Scheme 3. Plausible mechanism for defluoroborylation of aliphatic gem-difluoroalkenes. Scheme 4. CÀ F Bond borylation of gem-difluoroalkenes. Scheme 5. Copper-catalyzed trans-selective monodefluoroborylation of various gem-difluoroalkenes. Scheme 6. CÀ F Bond borylation of gem-difluoroalkenes. Scheme 7. Copper-catalyzed tunable multi-borylation reactions of gem-difluoroalkenes. In parentheses the ratio of 22, 23 and 24 is reported. Scheme 8. Stereoselective defluorinative borylation and silylation of gem-difluoroalkenes. Scheme 9. a) Synthesis of fluorinated vinylsilanes from gem-difluoro/ polyfluoroalkenes. b) Cross-coupling reaction of 29 b and iodobenzene. Scheme 10. Nickel-catalyzed fluoroalkenylation of unactivated alkylbromides. rr = The regioisomeric ratio of the benzylic fluoroÀ alkenylation product to the other regioisomers. DMA = N,N-Dimethylacetamide. Scheme 14. Iron-catalyzed defluorinative cross-coupling of donor alkenes with gem-difluoroalkenes. Dibm = diisobutyrylmethane. Scheme 15. Nickel-catalyzed reductive aryl monofluoroalkenylation of alkenes. Scheme 16. Plausible mechanism for reductive aryl monofluoroalkenylation of gem-difluoroalkenes. Scheme 17. Nickel-catalyzed hydroalkenylation of alkynes through oxidative cyclization and β-fluoride elimination. Scheme 28. Ruthenium-catalyzed fluoroal...

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Section: Synthesis Of Trifluoromethyl Derivativesmentioning

confidence: 99%

Section: Generation Of Trifluoromethanesmentioning

confidence: 99%