Dual Catalysis Relay: Coupling of Aldehydes and Alkenes Enabled by Visible-Light and NHC-Catalyzed Cross-Double C–H Functionalizations

Liu, Ming-Shang; Min, Lin; Chen, Bi-Hong; Shu, Wei

doi:10.1021/acscatal.1c02890

Cited by 59 publications

(32 citation statements)

References 63 publications

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“…Shortly thereafter, the group of Shu also reported the NHC/photoreox-catalyzed vinylation of aldehydes to obtain related products . Unlike the redox-neutral pathway developed by Studer, the Shu group introduced an oxidative coupling process by adding a stoichiometric amount of diphenoquinone as a two-electron oxidant to mediate the single-electron oxidation of both the Breslow intermediate and the sodium sulfinate (Scheme ).…”

Section: Ketyl Radicals Generated Via Single-electron Reduction Using...mentioning

confidence: 99%

Radical NHC Catalysis

2022

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Radical/radical cross-coupling reactions represent an efficient and straightforward approach for the construction of chemical bonds and accordingly have drawn increasing attention over the past decades. In order to achieve synthetically useful transformations, a persistent radical should be coupled with a transient radical in accordance with the persistent radical effect (PRE). However, known transient radicals outnumber by far the known types of free persistent radicals, which limits the widespread application of the PRE, until today. Thus, the development of efficient cross-coupling reactions between transient radicals has been in focus, and meanwhile transition-metal catalysis has been successfully implemented to artificially prolong radical lifetimes, allowing their utilization in formal radical/radical cross-couplings. Complementary research in the field recently uncovered that organocatalytically generated NHC-derived ketyl radicals are a type of catalytically generated free persistent radicals. NHC-catalyzed radical transformations of aldehydes and carboxylic acid derivatives have enabled the disclosure of an ever-increasing number of interesting reactions, which are different from traditional NHC-catalyzed ionic processes, offering otherwise inaccessible activation modes. These discoveries have opened a door to NHC organocatalysis for the manipulation of radical reactions. Due to its obvious potential in synthetic organic chemistry, it is timely to provide a perspective on this emerging field.

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Section: Ketyl Radicals Generated Via Single-electron Reduction Using...mentioning

confidence: 99%

Radical NHC Catalysis

2022

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“…Different from previous redox-neutral protocols, Shu reported a NHC-1 and PC-2 (PC-2 = Ru(bpy)3Cl2 • 6H2O) cocatalyzed oxidative cross-coupling of aldehydes with alkenes (Scheme 18). 31 Sodium benzenesulfinate acting as a radical precursor initiates 1,2-sulfonylacylation of alkenes, but the obtained β-sulfonyl ketone is unstable under the basic reaction condition, affording α, β-unsaturated ketone as final product. The usage of diphenoquinone is essential for the success of this reaction, which plays an intriguing two-fold role in the reaction, as an electron acceptor as well as a radical reservoir for the radical coupling enabling the C-C forming process.…”

Section: Othersmentioning

confidence: 99%

Research Progress on N-Heterocyclic Carbene Catalyzed Reactions for Synthesizing Ketones through Radical Mechanism

Wan

Yang

2022

Synthesis

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Recently NHC-catalyzed radical cross-coupling reactions have sprung up, which provided an efficient method to access ketones from aldehydes or carboxylic acid derivatives with sp3-hybridized carbon radical precursors. It has indirectly solved the limitation of coupling partners scope in NHC umpolung catalysis of aldehydes. In this short review, we present some of the recent advances in NHC-catalyzed radical reactions, with a focus on the construction of C-C(CO) bond.

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“…Shu and co‐workers developed an intermolecular vinylation of aldehydes 43 using alkenes 44 as the vinylating reagents through sequential two‐fold C−H functionalization (Scheme 15). [20] This protocol involves the coupling of alkenes and aldehydes to construct C−C bonds by merging visible light and N ‐heterocyclic carbene catalysis. The initial reaction was performed using 4‐methylbenzaldehyde and 4‐methoxystyrene as the model substrates.…”

Section: Functionalization Of Unactivated Olefins Via Visible‐light P...mentioning

confidence: 99%

Recent Advances in Mono‐ and Difunctionalization of Unactivated Olefins

et al. 2021

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Olefins are synthetically useful building blocks in modern organic synthesis. Direct functionalization of olefins; represent one of the most explored transformations in synthetic chemistry due to their easy availability and reactivity towards large number of reactants affording diverse range of organic compounds. In recent times, the development of new protocols for the functionalization of olefins is a growing realm. A plethora of olefin functionalization methodologies have been reported in the literature through ionic and free radical mechanisms including single electron transfer (SET) in the last two decades. This review gives an overview of mono-and difunctionalization of unactivated olefins, with an emphasis on the mechanistic details. Functionalization of Unactivated Olefins via Visible-Light Photocatalysis Iridium Photo-Catalyzed Reactions CarbofunctionalizationGlorius and co-workers reported an efficient visible-light mediated three component dicarbofunctionalization of olefins 2 using simple benzylic Katritzky salts 1 as radical precursors (Scheme 1). [8] In this protocol, abundant styrenes, electron-rich heterocycles, and benzylic amines were successfully employed to afford a number of densely functionalized 1,1-diarylalkanes. The optimal reaction conditions for this reaction are [Ir-(dtbbpy)(ppy) 2 ](PF 6 ) (1 mol%) as the photocatalyst in MeCN under irradiation with visible light for 16 h. Under the optimum [a

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Dual Catalysis Relay: Coupling of Aldehydes and Alkenes Enabled by Visible-Light and NHC-Catalyzed Cross-Double C–H Functionalizations

Cited by 59 publications

References 63 publications

Radical NHC Catalysis

Radical NHC Catalysis

Research Progress on N-Heterocyclic Carbene Catalyzed Reactions for Synthesizing Ketones through Radical Mechanism

Recent Advances in Mono‐ and Difunctionalization of Unactivated Olefins

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