Direct Alkylation of Glycine Derivatives via Photoinduced Palladium Catalysis, Utilizing Intermolecular Hydrogen Atom Transfer Mediated by Alkyl Radicals

Yang, Sen; Hu, Hao; Li, Jun-hua; Chen, Ming

doi:10.1021/acscatal.3c04075

Cited by 23 publications

(2 citation statements)

References 68 publications

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“…Methyl radical can function as a new class of hydrogen atom abstractor suitable for C(sp 3 )À H functionalization because of its exceptionally high bond dissociation energy (BDE = 105 kcal/mol) [31] and unique nucleophilic nature. [32] Despite attractive properties, the generation of methyl radical, an sp 3 -hybridized carbon-centered radical, [33][34][35] is quite challenging; therefore, there have been very few reports on the use of methyl radical for the functionalization of C(sp 3 )À H bonds. In 2002, the Tomioka group was the first to demonstrate the use of methyl radical as a hydrogen atom abstractor for C(sp 3 )À H functionalization.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical C(sp³)−H Functionalization Using Acetic Acid as a Hydrogen Atom Transfer Reagent

Morii,

Watanabe,

Saga

et al. 2024

ChemElectroChem

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In this study, we developed a novel electrochemical protocol that enables the functionalization of inherently inert C(sp3)−H bonds. In this protocol, one‐electron oxidation of acetic acid was used to successfully generate methyl radical, which cleaves the benzylic C(sp3)−H bonds of the substrates via a hydrogen atom transfer (HAT) process, and further reaction with the formed species yields the targeted C(sp3)−H functionalized products. To the best of our knowledge, this is the first example of the use of acetic acid in a HAT process. Notably the reaction has environment‐friendly and fine atom economy nature: the reaction is driven by the electrochemical conditions in the absence of expensive or hazardous reagents, producing only gaseous small molecules, hydrogen, carbon dioxide, and methane, as side products.

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Section: Introductionmentioning

confidence: 99%

Electrochemical C(sp³)−H Functionalization Using Acetic Acid as a Hydrogen Atom Transfer Reagent

Morii,

Watanabe,

Saga

et al. 2024

ChemElectroChem

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“…In accordance with the results of the control experiments and previous studies on the vinylogous aldol reaction, − a possible mechanism for this UV-light-catalyzed tandem reaction is proposed as shown in Scheme A. Initially, under the irradiation of UV LEDs, an intermolecular hydrogen atom transfer (HAT) process between methylbenzophenone 1 (methyl group) and isatin 2 (carbonyl group) occurs to afford radical intermediate IM1 and radical intermediate IM2 . Then, the radical intermediate IM2 couples with radical intermediate IM1 to give vinylogous aldol product 4 , which is converted to key photoenol intermediate IM3 via a photoenolization process (1,5-HAT) .…”

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confidence: 99%

Tandem Vinylogous Aldol and Intramolecular [2 + 2] Cycloaddition toward Benzocyclobutenes by UV Light Photocatalysis

Tan,

Liu,

Zhou

et al. 2024

Org. Lett.

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A facile and efficient radical tandem vinylogous aldol and intramolecular [2 + 2] cycloaddition reaction for direct synthesis of cyclobutane-containing benzocyclobutenes (BCBs) under extremely mild conditions without using any photocatalysts is reported. This approach exhibited definite compatibility with functional groups and afforded new BCBs with excellent regioselectivity and high yields. Moreover, detailed mechanism studies were carried out both experimentally and theoretically. The readily accessible, low-cost, and ecofriendly nature of the developed strategy will endow it with attractive applications in organic and medicinal chemistry.

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Stabilized Carbon‐Centered Radical‐Mediated Carbosulfenylation of Styrenes: Modular Synthesis of Sulfur‐Containing Glycine and Peptide Derivatives

Yang,

Liu,

Xie

2024

Advanced Science

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Sulfur‐containing amino acids and peptides play critical roles in organisms. Thiol‐ene reactions between the thiol residues of L‐cysteine and the alkenyl fragments in the designed coupling partners serve as primary tools for constructing C─S bonds in the synthesis of unnatural sulfur‐containing amino acid derivatives. These reactions are favored due to the preference for hydrogen transfer from thiol to β‐sulfanyl carbon radical intermediates. In this paper, the study proposes utilizing carbon‐centered radicals stabilized by the capto‐dative effect, generated under photocatalytic conditions from N–aryl glycine derivatives. The aim is to compete with the thiol hydrogen, enabling radical C─C bond formation with β‐sulfanyl carbon radicals. This protocol is robust in the presence of air and water, offers significant potential as a modular and efficient platform for synthesizing sulfur‐containing amino acids and modifying peptides, particularly with abundant disulfides and styrenes.

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Direct Alkylation of Glycine Derivatives via Photoinduced Palladium Catalysis, Utilizing Intermolecular Hydrogen Atom Transfer Mediated by Alkyl Radicals

Cited by 23 publications

References 68 publications

Electrochemical C(sp³)−H Functionalization Using Acetic Acid as a Hydrogen Atom Transfer Reagent

Electrochemical C(sp³)−H Functionalization Using Acetic Acid as a Hydrogen Atom Transfer Reagent

Tandem Vinylogous Aldol and Intramolecular [2 + 2] Cycloaddition toward Benzocyclobutenes by UV Light Photocatalysis

Stabilized Carbon‐Centered Radical‐Mediated Carbosulfenylation of Styrenes: Modular Synthesis of Sulfur‐Containing Glycine and Peptide Derivatives

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Direct Alkylation of Glycine Derivatives via Photoinduced Palladium Catalysis, Utilizing Intermolecular Hydrogen Atom Transfer Mediated by Alkyl Radicals

Cited by 23 publications

References 68 publications

Electrochemical C(sp3)−H Functionalization Using Acetic Acid as a Hydrogen Atom Transfer Reagent

Electrochemical C(sp3)−H Functionalization Using Acetic Acid as a Hydrogen Atom Transfer Reagent

Tandem Vinylogous Aldol and Intramolecular [2 + 2] Cycloaddition toward Benzocyclobutenes by UV Light Photocatalysis

Stabilized Carbon‐Centered Radical‐Mediated Carbosulfenylation of Styrenes: Modular Synthesis of Sulfur‐Containing Glycine and Peptide Derivatives

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Electrochemical C(sp³)−H Functionalization Using Acetic Acid as a Hydrogen Atom Transfer Reagent

Electrochemical C(sp³)−H Functionalization Using Acetic Acid as a Hydrogen Atom Transfer Reagent