Ni-catalyzed migratory fluoro-alkenylation of unactivated alkyl bromides with <i>gem</i>-difluoroalkenes

Lu, Zhou; Zhu, Caixia; Bi, Peijia; Feng, Chao

doi:10.1039/c8sc04162h

Cited by 101 publications

(33 citation statements)

References 65 publications

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“…In addition, reaction of vinyl fluoride 70 led to the formation of vinyl boronic ester 71 . Since direct cross coupling with vinyl fluorides is slow at ambient temperatures, it is suggested that the product formation occurs via 1,2‐elimination of the corresponding alkyl‐[Ni]‐complex . With respect to the mechanistic proposal for the reaction in toluene, it was observed that use of α‐methyl styrene ( 72 ) led to products resulting from a Heck‐type reaction ( 74 ) and hydroarylation ( 75 ).…”

Section: Methodsmentioning

confidence: 99%

Nickel‐Catalyzed Arylboration of Alkenylarenes: Synthesis of Boron‐Substituted Quaternary Carbons and Regiodivergent Reactions

et al. 2019

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A method for the construction of boron‐substituted quaternary carbons or diarylquaternary carbons by arylboration of highly substituted alkenylarenes is presented. A wide range of alkenes and arylbromides can participate in this reaction thus allowing for a diverse assortment of products to be prepared. In addition, a solvent dependent regiodivergent arylboration of 1,2‐disubstituted alkenylarenes is presented, thus greatly increasing the scope of products that can be accessed.

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Section: Methodsmentioning

confidence: 99%

Nickel‐Catalyzed Arylboration of Alkenylarenes: Synthesis of Boron‐Substituted Quaternary Carbons and Regiodivergent Reactions

et al. 2019

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“…gem-Difluoroalkenes reacted with CO 2 in the presence of alkenylboronic acid pinacol esters using a Cu I -based catalyst system and Xantphos as a ligand to afford a variety of valuable α-fluoroacrylic acids and α-fluoroacrylates (20, Scheme 6). [15] This one-pot formal ipso monocarboxylation of the CÀ F bond occured with high (Z)-selectivity and probably involved fluorinated boronate esters (19) as the key intermediate.…”

Section: Borylation and Silylationmentioning

confidence: 97%

“…A regio‐ and stereoselective convenient nickel‐catalyzed reductive coupling reaction of unactivated alkyl bromides with gem ‐difluoroalkenes generates α ‐benzyl fluoroalkenes (Scheme ) . This reaction delivered diversely functionalized monofluoroalkenyl derivatives ( 40 ) through a distinctive catalytic cycle that combined alkyl−Ni chain‐walking with defluorinative coupling.…”

Section: Reactions Proceeding Via β‐Fluoride Eliminationmentioning

confidence: 99%

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

Koley

Altman

2020

Israel Journal of Chemistry

131

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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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“…Inspired by a series of related Ni‐catalyzed remote functionalization techniques with a different set of electrophilic partners, Feng's group recently described the means to forge C−C bonds by combining unactivated alkyl bromides with gem ‐difluoroalkenes as coupling counterparts (Scheme ) . As for Zhu and Yin's protocols, the reaction took place at the benzylic sp 3 C−H site.…”

Section: Ni‐catalyzed Remote Sp3 Functionalizationmentioning

confidence: 99%

Tackling Remote sp³ C−H Functionalization via Ni‐Catalyzed “chain‐walking” Reactions

Janssen‐Müller

Sahoo

Sun

et al. 2019

Israel Journal of Chemistry

177

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Nickel catalysts have recently played an important role for rapidly and reliably converting feedstock chemicals into valuable compounds of interest for both pharmaceutical and academic laboratories. Herein, we summarize the recent advances on the ability of nickel catalysts to trigger olefin isomerization via "chain-walking", causing a displacement of the nickel catalyst throughout the alkyl chain while opening up new grounds for forging CÀ C and C-heteroatom linkages at remote, yet unfunctionalized, sp 3 CÀ H bonds. Scheme 3. Ni/L1-catalyzed remote hydroarylation of olefins Scheme 4. Ni/L2-catalyzed isomerization/hydroalkylation Scheme 5. Ni-catalyzed remote hydroarylation of olefins with ArI.Review Isr. J. Chem. 2020, 60, 195 -206 Scheme 15. Site-selective Ni-catalyzed reductive carboxylation of alkyl halides at remote sp 3 CÀ H sites. Scheme 16. Site-selective photochemical Ni-catalyzed carboxylation of alkyl halides at remote sp 3 CÀ H bonds. Scheme 17. Site-selective Ni-catalyzed carboxylation of olefins at remote sp 3 CÀ H sites with water as hydride source.

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Ni-catalyzed migratory fluoro-alkenylation of unactivated alkyl bromides with gem-difluoroalkenes

Abstract: A migratory fluoro-alkenylation of unactivated alkyl bromides is reported; the reaction is enabled by fluorine effects and involves an alkyl nickel chain-walking mechanism.

Cited by 101 publications

References 65 publications

Nickel‐Catalyzed Arylboration of Alkenylarenes: Synthesis of Boron‐Substituted Quaternary Carbons and Regiodivergent Reactions

Nickel‐Catalyzed Arylboration of Alkenylarenes: Synthesis of Boron‐Substituted Quaternary Carbons and Regiodivergent Reactions

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

Tackling Remote sp³ C−H Functionalization via Ni‐Catalyzed “chain‐walking” Reactions

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Ni-catalyzed migratory fluoro-alkenylation of unactivated alkyl bromides with gem-difluoroalkenes

Abstract: A migratory fluoro-alkenylation of unactivated alkyl bromides is reported; the reaction is enabled by fluorine effects and involves an alkyl nickel chain-walking mechanism.

Cited by 101 publications

References 65 publications

Nickel‐Catalyzed Arylboration of Alkenylarenes: Synthesis of Boron‐Substituted Quaternary Carbons and Regiodivergent Reactions

Nickel‐Catalyzed Arylboration of Alkenylarenes: Synthesis of Boron‐Substituted Quaternary Carbons and Regiodivergent Reactions

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

Tackling Remote sp3 C−H Functionalization via Ni‐Catalyzed “chain‐walking” Reactions

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Tackling Remote sp³ C−H Functionalization via Ni‐Catalyzed “chain‐walking” Reactions