Decarboxylative C–C and C–N Bond Formation by Ligand‐Accelerated Iron Photocatalysis

Feng, Guang‐Shou; Wang, Xiaofei; Jin, Jian

doi:10.1002/ejoc.201901381

Cited by 94 publications

(72 citation statements)

References 39 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Jin's group has described the use of photoexcited Fe-catalyzed decarboxylative coupling to form C-N bonds in hydrazines (Scheme 76). 48 Mechanistically (Scheme 77), this visible-light-excited redox-neutral process was believed to be similar to the C(sp 3 )-C(sp 3 ) coupling developed by the same group (see Scheme 74). 48 Scheme 76 Photoexcited Fe-catalyzed decarboxylative coupling to form hydrazines H. Chen et al…”

Section: Fe-catalyzed Decarboxylative C-n Bond Formationmentioning

confidence: 84%

“…Under visible-light irradiation, carboxylic acids underwent a radical decarboxylative reaction with 2-arylidenemalononitrile in the presence of an Fe catalyst (Scheme 73). 48 Different from the oxidative C(sp 3 )-C(sp 2 ) couplings (see Scheme 65), 45 this protocol was redox-neutral in which the oxidation of Fe II back to Fe III was realized by the electron-deficient radical intermediates (Scheme 74): Fe III 74.1 coordinates with carboxylic acid 74.2 to form Fe III -carboxylate complex 74.3, which is photoexcited and undergoes an intramolecular charge-transfer event to generate Fe II 74.4 and carboxyl radical 74.5. This radical releases CO 2 to become alkyl radical 74.6.…”

Section: Review Synthesismentioning

confidence: 99%

See 1 more Smart Citation

Recent Progress in Radical Decarboxylative Functionalizations Enabled by Transition-Metal (Ni, Cu, Fe, Co or Cr) Catalysis

2020

View full text Add to dashboard Cite

Aliphatic carboxylic acids are abundant in natural and synthetic sources and are widely used as connection points in many chemical transformations. Radical decarboxylative functionalization promoted by transition-metal catalysis has achieved great success, enabling carboxylic acids to be easily transformed into a wide variety of products. Herein, we highlight the recent advances made on transition-metal (Ni, Cu, Fe, Co or Cr) catalyzed C–X (X = C, N, H, O, B, or Si) bond formation as well as syntheses of ketones, amino acids, alcohols, ethers and difluoromethyl derivatives via radical decarboxylation of carboxylic acids or their derivatives, including, among others, redox-active esters (RAEs), anhydrides, and diacyl peroxides.1 Introduction2 Ni-Catalyzed Decarboxylative Functionalizations3 Cu-Catalyzed Decarboxylative Functionalizations4 Fe-Catalyzed Decarboxylative Functionalizations5 Co- and Cr-Catalyzed Decarboxylative Functionalizations6 Conclusions

show abstract

Section: Fe-catalyzed Decarboxylative C-n Bond Formationmentioning

confidence: 84%

Section: Review Synthesismentioning

confidence: 99%

Recent Progress in Radical Decarboxylative Functionalizations Enabled by Transition-Metal (Ni, Cu, Fe, Co or Cr) Catalysis

2020

View full text Add to dashboard Cite

show abstract

“…With continuous interest in such iron photocatalysis, Jin and co‐workers further achieved a redox‐neutral process with high decarboxylation efficiency by ligand modulation, which enabled the C−C and C−N bond formation (Scheme 12 b). [26a] In both cases (Scheme 12 a and b), the reaction was inhibited by the addition of a free radical scavenger, indicating the involvement of radical intermediates. The light/dark experiments demonstrated that the constant irradiation of visible light was necessary to drive the alkylation to completion.…”

Section: Light‐induced Iron Photoredox Catalysismentioning

confidence: 96%

Light Runs Across Iron Catalysts in Organic Transformations

Zhou

Meng

et al. 2020

Chemistry A European J

View full text Add to dashboard Cite

Over the past decades, organometallic complexes with precious elements, such as ruthenium and iridium, are widelyu sed as visible-light photoredox catalysts. Recently,m ore and more complexes based on earthabundant andi nexpensive elementsh ave been used as sensitizers in photochemistry.A lthough the photoexcited state lifetimes of iron complexes are typically shortert han those of traditional photosensitizers, the utilization of iron catalysts in photochemistry has sprung up owing to their abundance, low price, nontoxicity,a nd novel properties, including exhibiting ligand to metal charge transfer states. This concept focuses on recent advances in light-driven iron catalysis in organic transformations, including iron/ photoredox dual catalysis,l ight-inducedi ron photoredox catalysis and light-induced generation of active iron catalysts. The prospectf or the future of this field is also discussed.

show abstract

“…Jin's group has developed an alternative protocol for the decarboxylative C-N coupling reaction using an iron catalyst prepared in situ by complexation of Fe 2 (SO 4 ) 3 with a di-(2-picolyl)amine ligand (Scheme 52). 56 Azodicarboxylates and carboxylic acids were successfully coupled to give aliphatic amines. The oxidation of Fe(II) back to Fe(III) by the electron-deficient radical intermediates is proposed to be the key process for the redox-neutral coupling reaction.…”

Section: Scheme 51 Aminodecarboxylation Of Carboxylic Acidsmentioning

confidence: 99%

Recent Advances in Photocatalytic C–N Bond Coupling Reactions

Chan

Chow

2020

Synthesis

View full text Add to dashboard Cite

Catalytic C–N bond formation is one of the major research topics in synthetic chemistry owing to the ubiquity of amino groups in natural products, synthetic intermediates and pharmaceutical agents. In parallel with well-established metal-catalyzed C–N bond coupling protocols, photocatalytic reactions have recently emerged as efficient and selective alternatives for the construction of C–N bonds. In this review, the progress made on photocatalytic C–N bond coupling reactions between 2012 and February 2020 is summarized.1 Introduction1.1 General Mechanisms for Photoredox Catalysis1.2 Pioneering Work2 C(sp2)–N Bond Formation2.1 Protocols Involving an External Oxidant2.2 Oxidant-Free Protocols3 C(sp3)–N Bond Formation3.1 Direct Radical–Radical Coupling3.2 Addition Reactions to Alkenes3.3 Reductive Amination of Carbonyl Compounds3.4 Decarboxylative Amination4 Cyclization Reactions4.1 C(sp2)–N Heterocycle Formation4.2 C(sp3)–N Heterocycle Formation5 Other Examples6 Conclusion and Outlook

show abstract

Decarboxylative C–C and C–N Bond Formation by Ligand‐Accelerated Iron Photocatalysis

Cited by 94 publications

References 39 publications

Recent Progress in Radical Decarboxylative Functionalizations Enabled by Transition-Metal (Ni, Cu, Fe, Co or Cr) Catalysis

Recent Progress in Radical Decarboxylative Functionalizations Enabled by Transition-Metal (Ni, Cu, Fe, Co or Cr) Catalysis

Light Runs Across Iron Catalysts in Organic Transformations

Recent Advances in Photocatalytic C–N Bond Coupling Reactions

Contact Info

Product

Resources

About