Visible light photocatalytic decarboxylative monofluoroalkenylation of α-amino acids with gem-difluoroalkenes

Li, Jingjing; Lefebvre, Quentin; Yang, Haijun; Zhao, Yufen; Fu, Hua

doi:10.1039/c7cc05758j

Cited by 88 publications

(32 citation statements)

References 47 publications

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“…A visible light‐mediated photocatalytic decarboxylative reaction of N ‐protected α ‐amino acids ( 196 ) with gem ‐difluoroalkenes ( 195 ) generated the corresponding α ‐amino monofluoroalkenes ( 197 ) at room temperature (Scheme ) . In this reaction, reduction of the gem ‐difluoroalkene generated an active radical intermediate, which coupled with the α ‐amino radical (generated by the oxidative decarboxylation of the amino acid) to afford the final monofluoroalkenylated product.…”

Section: Photocatalytic Reductive C−f Bond Functionalizationmentioning

confidence: 99%

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

Koley

Altman

2020

Israel Journal of Chemistry

124

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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: Photocatalytic Reductive C−f Bond Functionalizationmentioning

confidence: 99%

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

Koley

Altman

2020

Israel Journal of Chemistry

124

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“…80 Following this report, the Fu group realized that N-protected -amino acids could be coupled with gem-difluoroalkenes to yield 3-aryl-2-fluoroprop-2-en-1-amines 64 (Scheme 13). 81 The protocol tolerated a range of amino acids, such as N-Boc-glycine, N-Bocalanine, N-Boc-phenylalanine, and N-Boc-serine, as well as numerous functional groups on the gem-difluoroalkene coupling partner including halogens, ester, ether, thioether, sulfonyl, and sulfonamide functionalities. The suggested mechanism involves base-mediated oxidation of the N-protected -amino acid 54 by the excited photocatalyst (*Ir III ) to deliver -amino radical 56.…”

Section: Review Syn Thesismentioning

confidence: 99%

Recent Advances in Photoredox Catalysis Enabled Functionalization of α-Amino Acids and Peptides: Concepts, Strategies and Mechanisms

et al. 2019

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The selective modification of α-amino acids and peptides constitutes a pivotal arena for accessing new peptide-based materials and therapeutics. In recent years, visible light photoredox catalysis has appeared as a powerful platform for the activation of small molecules via single-electron transfer events, allowing previously inaccessible reaction pathways to be explored. This review outlines the recent advances, mechanistic underpinnings, and opportunities of applying photoredox catalysis to the expansion of the synthetic repertoire for the modification of specific amino acid residues.1 Introduction2 Visible-Light-Mediated Functionalization of α-Amino Acids2.1 Decarboxylative Functionalization Involving Redox-Active Esters2.2 Direct Decarboxylative Coupling Strategies2.3 Hypervalent Iodine Reagents2.4 Dual Photoredox and Transition-Metal Catalysis2.5 Amination and Deamination Strategies3 Photoinduced Peptide Diversification3.1 Gese-Type Bioconjugation Methods3.2 Peptide Macrocyclization through Photoredox Catalysis3.3 Biomolecule Conjugation through Arylation3.4 C–H Functionalization Manifolds4 Conclusions and Outlook

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“…Fu's group developed a mild and practical visible light photocatalytic decarboxylative monofluoroalkenylation of N ‐protected α‐amino acids 86 with gem ‐difluoroalkenes 87 (Scheme ) . The reaction easily proceeded under visible light photocatalysis at room temperature with high efficiency and tolerance of various functional groups.…”

Section: Decarboxylative Reactions Of α‐Amino Acids Via Radical Pathwaysmentioning

confidence: 99%

Recent Advances on Diverse Decarboxylative Reactions of Amino Acids

et al. 2019

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This review aims to report recent advances on decarboxylative reactions of amino acids catalyzed by transitionm etals or non-metals and the growing opportunities they present in the construction of complexc hemical scaffolds for applications encompassing natural product synthesis, synthetic methodology development, and functional materials. Different decarboxylative reactions have been highlighted such as radical, photoredox and metal and metal-free coupling reactions.e tc. Ther eview is divided into two main sections:o ne deals with reactions via radical pathways andt he other via azomethine ylide pathways.T he reactions have been discussed in more detail with particular emphasis on their useful applications andm echanistic illustrations.

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Visible light photocatalytic decarboxylative monofluoroalkenylation of α-amino acids with gem-difluoroalkenes

Abstract: A novel, efficient and general visible-light photocatalytic decarboxylative monofluoroalkenylation of N-protected α-amino acids with gem-difluoroalkenes is reported, affording the corresponding α-amino monofluoroalkenes.

Cited by 88 publications

References 47 publications

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

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

Recent Advances in Photoredox Catalysis Enabled Functionalization of α-Amino Acids and Peptides: Concepts, Strategies and Mechanisms

Recent Advances on Diverse Decarboxylative Reactions of Amino Acids

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