Nucleophilic (Radio)Fluorination of Redox-Active Esters via Radical-Polar Crossover Enabled by Photoredox Catalysis

Webb, Eric; Park, John B.; Cole, Erin L.; Donnelly, David J.; Bonacorsi, Samuel J.; Ewing, William R.; Doyle, Abigail G.

doi:10.1021/jacs.0c03125

Cited by 141 publications

(95 citation statements)

References 83 publications

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“…This was demonstrated by Doyle and co‐workers, who used inexpensive triethylamine trihydrofluoride (Et 3 N . 3HF) as a nucleophilic fluoride source in an Ir(III)‐based photoredox catalysis (Scheme 28A) [244] . The reaction gives moderate to high yields for tertiary and α‐aryl/heteroatom‐substituted NHPI esters and does not extend to inactivated primary or secondary substrates (Scheme 28C).…”

Section: Decarboxylative C‐halogen Bond Formationmentioning

confidence: 99%

Decarboxylation‐Initiated Intermolecular Carbon‐Heteroatom Bond Formation

Zeng¹,

Feceu

Sivendran

et al. 2021

Adv Synth Catal

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Carboxylic acids are among the most used feedstock chemicals due to their great structural diversity and easy handling. The use of carboxylic acids and their derivatives in decarboxylative couplings has proven to be a valuable tool for the construction of C−C and C‐heteroatom bonds. This synthetic strategy provides a complementary bond disconnection to traditional cross‐coupling methods. In this review, we provide a comprehensive overview of decarboxylation‐initiated intermolecular C‐heteroatom bond formation, outlining several main mechanistic concepts combined with early examples and highlighting the achievements made in the past decade until January 2021. In these reactions, carboxylic acids and their derivatives undergo initial decarboxylation and then react with other heteroatom electrophiles and nucleophiles, thus replacing the carboxylate group with a valuable and prevalent heteroatom functionality.

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Section: Decarboxylative C‐halogen Bond Formationmentioning

confidence: 99%

Decarboxylation‐Initiated Intermolecular Carbon‐Heteroatom Bond Formation

Zeng¹,

Feceu

Sivendran

et al. 2021

Adv Synth Catal

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“…The products of decarboxylative iodination can be further used to construct C-O, C-N, C-F, and C-SCN bonds, allowing their subsequent use without requiring the expensive transition metals [38][39][40][41] . Concept of the photoactivation of an electron donor-acceptor encounter complex in a solvent cage for radical generation that can be used in the design of photocatalysis systems.…”

Section: Scheme 1 Radical Cyclization Experimentsmentioning

confidence: 99%

Triphenylphosphine-Catalyzed Alkylative Iododecarboxylation with Lithium Iodide under Visible Light

Wang

Shang

2020

Org. Lett.

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Photoactivation of an electron donor-acceptor encounter complex in an organic solvent cage, a phenomenon that has been described in Mulliken theory, has been known for decades, but it has not been employed as a photoactivation step in the design of photocatalysis for organic synthesis until recent years. We report herein an iododecarboxylation reaction that applies this concept for photoactivation by using a catalyst to facilitate electron transfer and to suppress back electron transfer in the photoexcited state. Under irradiation of 456 nm blue light-emitting diodes, PPh3 catalyzes the iododecarboxylation of aliphatic carboxylic acid-derived N-(acyloxy)phthalimide with lithium iodide as iodine source. The reaction delivers primary, secondary, and bridgehead tertiary alkyl iodides in acetone solvent, and the alkyl iodide products were easily used to generate C-N, CO , C-F, and C-S bonds to allow various decarboxylative transformations without using transition-metal or organic dye-based photocatalysts. This protocol is applicable to redox-active esters derived from various natural products and pharmaceuticals.

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“…25). 167 The excited PC is proposed to be oxidatively quenched by this redox-active ester, forming an alkyl radical (Fig. 26).…”

Section: Photoinduced Decarboxylation Of Carboxylic Acids In the Formation Of C-c And C-x Bonds In A Reductive Quenching Mechanismmentioning

confidence: 99%

Organic thermally activated delayed fluorescence (TADF) compounds used in photocatalysis

2021

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Nucleophilic (Radio)Fluorination of Redox-Active Esters via Radical-Polar Crossover Enabled by Photoredox Catalysis

Cited by 141 publications

References 83 publications

Decarboxylation‐Initiated Intermolecular Carbon‐Heteroatom Bond Formation

Decarboxylation‐Initiated Intermolecular Carbon‐Heteroatom Bond Formation

Triphenylphosphine-Catalyzed Alkylative Iododecarboxylation with Lithium Iodide under Visible Light

Organic thermally activated delayed fluorescence (TADF) compounds used in photocatalysis

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