Visible-Light-Induced Radical Acylation of Imines with α-Ketoacids Enabled by Electron-Donor–Acceptor Complexes

Zhang, Hong‐Hao; Yu, Shouyun

doi:10.1021/acs.orglett.9b01169

Cited by 54 publications

(22 citation statements)

References 94 publications

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“…In 2019, the Yu group also reported a catalyst-free visible-light-induced radical acylation of aldimines with α-ketoacids enabled by the generation of an EDA complex ( Scheme 325 ). 893 This catalyst-free protocol was carried out with 1 equiv of imine and 1.5 equiv of α-ketoacid in CH 2 Cl 2 solvent under irradiation with blue light. Under these reaction conditions, 30 examples of the desired α-amino ketone were synthesized, with yields ranging from 50% to 90%.…”

Section: Reductive Transformations Of Carbonyls Imines and Other X=y Functional Groups Through Photochemical And Electrochemical Pcet Promentioning

confidence: 99%

Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis

et al. 2021

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We present here a review of the photochemical and electrochemical applications of multi-site proton-coupled electron transfer (MS-PCET) in organic synthesis. MS-PCETs are redox mechanisms in which both an electron and a proton are exchanged together, often in a concerted elementary step. As such, MS-PCET can function as a non-classical mechanism for homolytic bond activation, providing opportunities to generate synthetically useful free radical intermediates directly from a wide variety of common organic functional groups. We present an introduction to MS-PCET and a practitioner’s guide to reaction design, with an emphasis on the unique energetic and selectivity features that are characteristic of this reaction class. We then present chapters on oxidative N–H, O–H, S–H, and C–H bond homolysis methods, for the generation of the corresponding neutral radical species. Then, chapters for reductive PCET activations involving carbonyl, imine, other X=Y π-systems, and heteroarenes, where neutral ketyl, α-amino, and heteroarene-derived radicals can be generated. Finally, we present chapters on the applications of MS-PCET in asymmetric catalysis and in materials and device applications. Within each chapter, we subdivide by the functional group undergoing homolysis, and thereafter by the type of transformation being promoted. Methods published prior to the end of December 2020 are presented.

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Section: Reductive Transformations Of Carbonyls Imines and Other X=y Functional Groups Through Photochemical And Electrochemical Pcet Promentioning

confidence: 99%

Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis

et al. 2021

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“…A conceptually different methodology employed the excitation of an EDA complex between an in situ formed imine and phenyl oxalate to generate a pair of radicals. 235 Upon CO 2 extrusion, radical-radical coupling happens, forming an aaminoketone in 62% yield (gram scale reaction: 1.16 g). Despite being mainly applied to preformed imines, the prospect of using this strategy in a multicomponent way is appealing (Scheme 127).…”

Section: Scheme 89mentioning

confidence: 99%

Multicomponent reactions and photo/electrochemistry join forces: atom economy meets energy efficiency

et al. 2022

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“…[9] In the same year, Yu group demonstrated the radical acylation of imines 10 using α-ketoacids 1 enabled via electron-donor-acceptor complexes by visible-light catalysis (Scheme 1e). [10] Prabhu et al reported the direct decarboxylative acylation of electron deficient heteroarenes 12 using α-ketoacids 1 by photocatalysis (Scheme 1f). [11] In 2020, Li group reported the photoredoxcatalyzed synthesis of ketones 15 from arylhalides 14 using αketoacid 1 as an acylating agent (Scheme 1g).…”

Section: α-Keto Acidsmentioning

confidence: 99%

Alternative and Uncommon Acylating Agents – An Alive and Kicking Methodology

Sivaraj

Gandhi

2021

Chemistry An Asian Journal

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Functionalizing and derivatising organic molecules is a centerpiece in organic synthesis. Succinctly manipulating and installing acyl moieties in organic molecules spurred the interest of chemists owing to its occurrence in natural products, bioactive molecules, pharmaceuticals, and advanced materials. Traditionally, access to acylation reaction was achieved by Friedel-Crafts reaction, Schotten-Baumann, and Vilsmeier-Haack acylation, however, these protocols own pitfalls. Further to make the acylation process attractive and environmentally friendly, toluene, aldehydes, alcohols, α-keto acids, amines, amides, esters, ethers, nitriles, alkynes, alkenes, ketenes, N-acylbenzotriazoles, ketones, thioacids, oximes, thiazolium carbinols, PIDA, diacyl disulfides and acyl salts were used as an acyl surrogates/reagents. Amusingly, these acylating reagents are considered uncommon and alternative to carboxylic acids, acid chlorides and acetic anhydrides. This short review aims to encompass the usage of acylating agents in transition-metal, metal-free, light-driven and other demanding conditions, and thus reveals their practicality.

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Visible-Light-Induced Radical Acylation of Imines with α-Ketoacids Enabled by Electron-Donor–Acceptor Complexes

Cited by 54 publications

References 94 publications

Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis

Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis

Multicomponent reactions and photo/electrochemistry join forces: atom economy meets energy efficiency

Alternative and Uncommon Acylating Agents – An Alive and Kicking Methodology

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