Tandem Photoredox Catalysis: Enabling Carbonylative Amidation of Aryl and Alkylhalides

Forni, José Augusto; Micic, Nenad; Connell, Timothy U.; Weragoda, Geethika K.; Polyzos, Anastasios

doi:10.1002/ange.202006720

Cited by 8 publications

(1 citation statement)

References 90 publications

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“…The use of light of various wavelengths in organic synthesis has seen a dramatic resurgence in the past few years, with unusual bond disconnections to rapidly access complex molecular structures, including pharmaceuticals . The use of amine boranes, carbonylative amidation of aryl and alkyl halides, acylation of amines in water, amide generation from alcohols and amines, oxidative amidation of amines, and metal-free amidation of thioacids are a few recent examples that demonstrate the versatility of this technology for the synthesis of amides. From the process chemist’s point of view, one of the limitations of photoredox catalysis is related to its scalability in batch mode, but flow photochemistry has emerged as a viable option in recent years to facilitate its implementation on scale …”

Section: Discussionmentioning

confidence: 99%

Large-Scale Amidations in Process Chemistry: Practical Considerations for Reagent Selection and Reaction Execution

Magano

2022

Org. Process Res. Dev.

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This review describes the practical aspects involved in the implementation of large-scale amidations in process chemistry. Coupling reagent, base, additive, and solvent selections are critically analyzed to highlight their pros and cons. Other important factors to be considered on large scale, such as atom economy, cost, safety, and toxicity, are also examined. These concepts are then showcased through selected examples from the literature for the synthesis of active pharmaceutical ingredients.

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Section: Discussionmentioning

confidence: 99%

Large-Scale Amidations in Process Chemistry: Practical Considerations for Reagent Selection and Reaction Execution

Magano

2022

Org. Process Res. Dev.

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Generation of Oxyphosphonium Ions by Photoredox/Cobaloxime Catalysis for Scalable Amide and Peptide Synthesis in Batch and Continuous‐Flow

Chen

et al. 2021

Angewandte Chemie

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Phosphine-mediated deoxygenative nucleophilic substitutions,s uch as the Mitsunobu reaction, are of great importance in organic synthesis.H owever,t he conventional protocols require stoichiometric oxidants to trigger the formation of the oxyphosphonium intermediates for the subsequent nucleophilic additions.Through dual catalysis of photoredox and cobaloxime,w er ealized ar adical strategy for the catalytic formation of acyloxyphosphonium ions that enables direct amidation. The deoxygenative protocol exhibits abroad scope and has been used in the late-stage amidation of drug molecules.I na ddition to batch reactions,acontinuous-flow reactor was developed, enabling rapid peptide synthesis on gram scale.T he successful assembly of at etrapeptide on the solid support further demonstrated the versatility of this photocatalytic system. Moreover,e xperimental and computational studies are consistent with the hypothesis of acyloxyphosphonium ions being formed as the key intermediates.Scheme 1. P-assisted deoxygenative substitutions.

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Photo‐Excited Nickel‐Catalyzed Silyl‐Radical‐Mediated Direct Activation of Carbamoyl Chlorides To Access (Hetero)aryl Carbamides**

et al. 2022

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Amide bonds connect the amino acids in proteins and exist as a prevalent structural motif in biomolecules. Herein, we have exploited the concept of cross-electrophile coupling by merging the photo-redox and transition-metal catalysis to construct carbamides from superabundant (hetero)aryl halides along with commercially feasible carbamoyl chlorides. The success of this method relies on the prior formation of Ni II -aryl halide intermediates, which involves in a photoexcited Ni-halide homolysis event by energy transfer from aryl bromide and single-electron transfer from aryl chloride to assist generation of the vital carbamoyl radical. The breadth of application of this technique is demonstrated both in inter-as well as intramolecular routes for the synthesis of a plethora of (hetero)aryl carbamides with diverse functionalities, and biologically important benzolactams.

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Tandem Photoredox Catalysis: Enabling Carbonylative Amidation of Aryl and Alkylhalides

Cited by 8 publications

References 90 publications

Large-Scale Amidations in Process Chemistry: Practical Considerations for Reagent Selection and Reaction Execution

Large-Scale Amidations in Process Chemistry: Practical Considerations for Reagent Selection and Reaction Execution

Generation of Oxyphosphonium Ions by Photoredox/Cobaloxime Catalysis for Scalable Amide and Peptide Synthesis in Batch and Continuous‐Flow

Photo‐Excited Nickel‐Catalyzed Silyl‐Radical‐Mediated Direct Activation of Carbamoyl Chlorides To Access (Hetero)aryl Carbamides**

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