Catalytic cleavage and functionalization of bulky and inert Csp3–Csp3 bonds via a relayed proton-coupled electron transfer strategy

Liao, Ke; Wu, Fengjin; Chen, Jiean; Huang, Yong

doi:10.1016/j.xcrp.2022.100763

Cited by 14 publications

(13 citation statements)

References 52 publications

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“…Due to the reduced crowding at the benzylic carbon, benzyl radical addition was found to compete with the second SEO step. 34 Ring deconstruction was also feasible, albeit under slightly different conditions, to obtain the desired ring-opening products (Scheme 3F).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…While the methylated product ( 52 ) was isolated in 22% yield, the reaction was contaminated with a substantial amount of benzyl functionalization compound (Scheme E, 53 , 44% yield). Due to the reduced crowding at the benzylic carbon, benzyl radical addition was found to compete with the second SEO step . Ring deconstruction was also feasible, albeit under slightly different conditions, to obtain the desired ring-opening products (Scheme F).…”

Section: Resultsmentioning

confidence: 99%

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Photoredox Cleavage of a C_sp3–C_sp3 Bond in Aromatic Hydrocarbons

et al. 2023

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Functionalizing molecules through the selective cleavage of carbon–carbon bonds is an attractive approach in synthetic chemistry. Despite recent advances in both transition-metal catalysis and radical chemistry, the selective cleavage of inert Csp3–Csp3 bonds in hydrocarbon feedstocks remains challenging. Examples reported in the literature typically involve substrates containing redox functional groups or highly strained molecules. In this article, we present a straightforward protocol for the cleavage and functionalization of Csp3–Csp3 bonds in alkylbenzenes using photoredox catalysis. Our method employs two distinct bond scission pathways. For substrates with tertiary benzylic substituents, a carbocation-coupled electron transfer mechanism is prevalent. For substrates with primary or secondary benzylic substituents, a triple single-electron oxidation cascade is applicable. Our strategy offers a practical means of cleaving inert Csp3–Csp3 bonds in molecules without any heteroatoms, resulting in primary, secondary, tertiary, and benzylic radical species.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Photoredox Cleavage of a C_sp3–C_sp3 Bond in Aromatic Hydrocarbons

et al. 2023

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“…The sub-sequent reaction of the alkyl radical with electron-deficient systems, including pyridines, led to C-H functionalization (Scheme 17). 30 Ammonium persulfate was used as a stoichiometric oxidant. Finally, alkyl radicals were also generated from C(sp 3 )-H, followed by their addition to pyridines for substituted pyridines.…”

Section: Organic and Biomolecular Chemistry Reviewmentioning

confidence: 99%

“…The subsequent reaction of the alkyl radical with electron-deficient systems, including pyridines, led to C–H functionalization (Scheme 17). 30…”

Section: Direct Functionalizationmentioning

confidence: 99%

C–H functionalization of pyridines

et al. 2023

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“…The authors have cited additional references within the Supporting Information. [20][21][22][23][24][25][26][27][28]…”

Section: Supporting Informationmentioning

confidence: 99%

Photoinduced Pyridine N‐oxides Catalyzed Carbon Radical Generation from Alkylboronic Acids

Ascenzi‐Pettenuzzo,

Nganda,

Deng

2023

ChemCatChem

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Herein we report a protocol for the generation of alkyl carbon radicals from alkylboronic acids wherein photoexcited 4‐nitropyridine N‐oxide biradical features a catalyst to promote the nucleo‐homolytic substitution of boronic acids. With a wide range of readily available aliphatic boronic acids, including methyl boronic acid, the developed catalytic system demonstrates broad applicability for alkylation, amination, and cyanation.

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Catalytic cleavage and functionalization of bulky and inert Csp3–Csp3 bonds via a relayed proton-coupled electron transfer strategy

Cited by 14 publications

References 52 publications

Photoredox Cleavage of a C_sp3–C_sp3 Bond in Aromatic Hydrocarbons

Photoredox Cleavage of a C_sp3–C_sp3 Bond in Aromatic Hydrocarbons

C–H functionalization of pyridines

Photoinduced Pyridine N‐oxides Catalyzed Carbon Radical Generation from Alkylboronic Acids

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Catalytic cleavage and functionalization of bulky and inert Csp3–Csp3 bonds via a relayed proton-coupled electron transfer strategy

Cited by 14 publications

References 52 publications

Photoredox Cleavage of a Csp3–Csp3 Bond in Aromatic Hydrocarbons

Photoredox Cleavage of a Csp3–Csp3 Bond in Aromatic Hydrocarbons

C–H functionalization of pyridines

Photoinduced Pyridine N‐oxides Catalyzed Carbon Radical Generation from Alkylboronic Acids

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Product

Resources

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Photoredox Cleavage of a C_sp3–C_sp3 Bond in Aromatic Hydrocarbons

Photoredox Cleavage of a C_sp3–C_sp3 Bond in Aromatic Hydrocarbons