Intramolecular dehydrogenative amination of alkenes <i>via</i> dual organic photoredox and cobalt catalysis without a hydrogen acceptor

Yu, Wancong; Ren, Zi-Gang; Ma, Wei; Zheng, Haixue; Wu, Wangsuo; Xu, Peng‐Fei

doi:10.1039/d2gc02084j

Cited by 12 publications

(3 citation statements)

References 69 publications

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“…As illustrated in Figure , the irreversible oxidation potential value of 3-methylbut-2-en-1-yl (4-chlorophenyl)carbamate 1a was observed at +1.98 V (vs Ag/AgCl in CH 3 CN). Xu’s group reported that substrate 1a even without the double bond could also provide the same oxidation potential . The results above showed that the activation site is not in the double bond but probably in the N–H bond.…”

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confidence: 81%

“…Xu's group reported that substrate 1a even without the double bond could also provide the same oxidation potential. 11 The results above showed that the activation site is not in the double bond but probably in the N−H bond. Besides, irreversible oxidative and reductive peaks of such a copper catalytic system appeared, respectively, at −0.70 V and −0.97 V (vs Ag/AgCl in CH 3 CN), corresponding to the Cu(I)/Cu(II)/Cu(III) redox couple.…”

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confidence: 99%

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Photoinduced Copper-Catalyzed Aminoalkylation of Amino-Pendant Olefins

Zhang

et al. 2023

Org. Lett.

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The combination of photo and copper catalysts has emerged as a novel paradigm in organic catalysis, which provides access to the acceleration of chemical synthesis. Herein, we describe an aminoalkylation of amino-dependent olefins with maleimides through a cooperative photo/copper catalytic system. In this report, the strategy allows the generation of a broad complex of functionalized nitrogenous molecules including oxazolidinones, 2-pyrrolidones, imidazolidinones, thiazolidinones, pyridines, and piperidines in the absence of an external photosensitizer and base. The approach is achieved through a photoinduced Cu(I)/Cu(II)/Cu(III) complex species of nitrogen nucleophiles, intermolecular radical addition, and hydrogen atom transfer (HAT) processes. The plausible mechanism is investigated by a series of control experiments and theoretical tests, including radical scavenging experiments, deuterium labeling experiments, ultraviolet−visible absorption, and cyclic voltammetry (CV) tests.

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confidence: 81%

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confidence: 99%

Photoinduced Copper-Catalyzed Aminoalkylation of Amino-Pendant Olefins

Zhang

et al. 2023

Org. Lett.

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“…Furthermore, Xu et al also reported on the intramolecular dehydrogenative amination of alkenes through synergistic photoredox and cobaloxime catalysis, resulting in the formation of a diverse array of five-membered Nheterocycles. [51] Photoredox catalysis facilitates the formation of nitrogen radicals, which undergo 5-exo-trig cyclization to form a radical intermediate. This intermediate is subsequently captured by [Co II ] to generate [Co III ]À H and the dehydrogenative amination product.…”

Section: Cdc Of Olefinsmentioning

confidence: 99%

Biomimetic Photoexcited Cobaloxime Catalysis in Organic Synthesis

Dam,

Zuo,

Azofra

et al. 2024

Angewandte Chemie

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Drawing inspiration from nature has long been a cornerstone of chemical innovation, with natural systems offering a wealth of untapped potential for discovery. In this minireview, we delve into the burgeoning field of cobaloxime catalysis in organic synthesis, which mimic the catalytic activity of the natural organometallic alkylcobalamine enzymes. Our focus lies on elucidating the latest advancements in this area, as well as delineating the primary mechanistic pathways at play. By describing, and comparing these mechanisms, we provide a comprehensive overview of the current state‐of‐the‐art, while also shedding light on the key unresolved challenges that await further exploration.

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Photochemische Cobaltkatalysierte Synthese von Heterozyklen durch die Zykloisomerisierung Nichtaktivierter Olefine

Lindner,

Amberg,

Martini

et al. 2024

Angewandte Chemie

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We report a general, intramolecular cycloisomerization of unactivated olefins with pendant nucleophiles. The reaction proceeds under mild conditions and tolerates ethers, esters, protected amines, acetals, pyrazoles, carbamates, and arenes. It is amenable to N‐, O‐, as well as C‐nucleophiles, yielding a number of different heterocycles including, but not limited to, pyrrolidines, piperidines, oxazolidinones, and lactones. Use of both a benzothiazinoquinoxaline as organophotocatalyst and a Co‐salen catalyst obviates the need for stoichiometric oxidant or reductant. We showcase the utility of the protocol in late‐stage drug diversification and synthesis of several small natural products.

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Intramolecular dehydrogenative amination of alkenes via dual organic photoredox and cobalt catalysis without a hydrogen acceptor

Abstract: Direct C-H/N-H dehydrogenative coupling is a promising yet thermodynamically unfavorable transformation in the absence of sacrificial hydrogen acceptor. Herein, a conceptually novel oxidant-free dehydrogenative amination of alkenes through a synergistic...

Cited by 12 publications

References 69 publications

Photoinduced Copper-Catalyzed Aminoalkylation of Amino-Pendant Olefins

Photoinduced Copper-Catalyzed Aminoalkylation of Amino-Pendant Olefins

Biomimetic Photoexcited Cobaloxime Catalysis in Organic Synthesis

Photochemische Cobaltkatalysierte Synthese von Heterozyklen durch die Zykloisomerisierung Nichtaktivierter Olefine

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