Photoelectrochemical Asymmetric Catalysis Enables Enantioselective Heteroarylcyanation of Alkenes via C–H Functionalization

Lai, Xiao‐Li; Xu, Hai‐Chao

doi:10.1021/jacs.3c07146

Cited by 32 publications

(11 citation statements)

References 54 publications

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“…In 2023, Lai and Xu reported a photoelectrocatalytic protocol for the enantioselective heteroarylcyanation of styrene congeners with unactivated heteroarenes and TMSCN through C−H functionalization, which simultaneously introduces a heteroaryl group and a cyano group across the alkene moiety to give the corresponding α-cyano-β-heteroarylethylarenes 10B ( Figure 10B ) ( Lai and Xu, 2023 ). This process employs acridinium salt [Mes-Acr-Ph]BF 4 as photoredox catalyst, Cu(CN) 2 with a bisoxazoline ligand BOX I 3 as chiral electrocatalyst, 456 nm LEDs, and TMSCN as the CN source.…”

Section: Asymmetric Electrochemical Catalysismentioning

confidence: 99%

Recent advances in catalytic asymmetric synthesis

Garg,

Rendina,

Bendale

et al. 2024

Front. Chem.

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Asymmetric catalysis stands at the forefront of modern chemistry, serving as a cornerstone for the efficient creation of enantiopure chiral molecules characterized by their high selectivity. In this review, we delve into the realm of asymmetric catalytic reactions, which spans various methodologies, each contributing to the broader landscape of the enantioselective synthesis of chiral molecules. Transition metals play a central role as catalysts for a wide range of transformations with chiral ligands such as phosphines, N-heterocyclic carbenes (NHCs), etc., facilitating the formation of chiral C-C and C-X bonds, enabling precise control over stereochemistry. Enantioselective photocatalytic reactions leverage the power of light as a driving force for the synthesis of chiral molecules. Asymmetric electrocatalysis has emerged as a sustainable approach, being both atom-efficient and environmentally friendly, while offering a versatile toolkit for enantioselective reductions and oxidations. Biocatalysis relies on nature’s most efficient catalysts, i.e., enzymes, to provide exquisite selectivity, as well as a high tolerance for diverse functional groups under mild conditions. Thus, enzymatic optical resolution, kinetic resolution and dynamic kinetic resolution have revolutionized the production of enantiopure compounds. Enantioselective organocatalysis uses metal-free organocatalysts, consisting of modular chiral phosphorus, sulfur and nitrogen components, facilitating remarkably efficient and diverse enantioselective transformations. Additionally, unlocking traditionally unreactive C-H bonds through selective functionalization has expanded the arsenal of catalytic asymmetric synthesis, enabling the efficient and atom-economical construction of enantiopure chiral molecules. Incorporating flow chemistry into asymmetric catalysis has been transformative, as continuous flow systems provide precise control over reaction conditions, enhancing the efficiency and facilitating optimization. Researchers are increasingly adopting hybrid approaches that combine multiple strategies synergistically to tackle complex synthetic challenges. This convergence holds great promise, propelling the field of asymmetric catalysis forward and facilitating the efficient construction of complex molecules in enantiopure form. As these methodologies evolve and complement one another, they push the boundaries of what can be accomplished in catalytic asymmetric synthesis, leading to the discovery of novel, highly selective transformations which may lead to groundbreaking applications across various industries.

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Section: Asymmetric Electrochemical Catalysismentioning

confidence: 99%

Recent advances in catalytic asymmetric synthesis

Garg,

Rendina,

Bendale

et al. 2024

Front. Chem.

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“…Several pioneers, including Lambert, [6] Xu, [7] Lei [8] and Wickens, [9] have published particularly outstanding works in this regard, and using the catalytic cycle of a PC as an electron shuttle between the reactants and the anode [6][7][8]10] or cathode, [9,11] a super photooxidant [6,10] or photoreductant [9,11] could be generated in situ, with the mild electrode potential turned into an amplified excited-state potential. Alternatively, a photoactive hydrogen-atom-transfer mediator, such as CeCl 3 , [12][13][14] FeCl 3 , [15] aryl ketone, [16,17] decatungstate [18] or riboflavin, [19] is incorporated into the electrolysis to facilitate radical formation at the anode.…”

Section: Introductionmentioning

confidence: 99%

Self‐ or Acridinium‐Catalyzed Electrophotosynthesis of Thiocyanato Heterocycles from Activated Alkenes

Gong,

Ma,

et al. 2024

Adv Synth Catal

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While the emergence of electrophotochemistry provides opportunities, such a chemistry at this stage suffers from limited reaction types and high photocatalyst loadings. A self‐catalyzed electrophotosynthesis as well as one with a low photocatalyst loading is presented. These external‐oxidant‐free cyclizations are enabling and applicable to a range of activated alkenes, affording a diverse array of thiocyanato heterocycles including 4‐pyrrolin‐2‐ones, isoquinoline‐1,3‐diones, indolo[2,1‐a]isoquinolin‐6(5H)‐ones, benzoimidazo[2,1‐a]isoquinolin‐6(5H)‐ones and indolin‐2‐ones, and the protocols are amenable to the late‐stage diversification of complex molecular architectures as well as gram‐scale syntheses. Sunlight could serve as the light source, and the reaction could be conducted in an all‐solar‐driven mode using a commercially available photovoltaic panel to produce electricity.

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“…With the renaissance of electrosynthesis, the asymmetric electrocatalysis involving anodic oxidation has made significant progress in recent years. [49][50][51][52][53][54][55][56][57][58][59][60][61][62][63][64][65][66][67] However, there are few research focus on the asymmetric electrochemical reductive reactions https://doi.org/10.26434/chemrxiv-2024-zb3sh ORCID: https://orcid.org/0000-0003-2024-2122 Content not peer-reviewed by ChemRxiv. License: CC BY-NC-ND 4.0…”

Section: Introductionmentioning

confidence: 99%

Electrochemically driven Nickel-Catalyzed Enantioselective Reductive Conjugate (Hetero)Arylation of Enones

Ye,

Ma,

Zhang

et al. 2024

Preprint

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Herein, we report an electrochemical nickel-catalyzed enantioselective reductive conjugate (hetero)arylation of enones in an undivided cell with low-cost electrodes in the absence of external reductants. Aryl bromides/iodides/triflates or vinyl bromides were employed as electrophilic reagents for the efficient preparation of more than 50 valuable β-arylated ketones in a simple manner (up to 97% yield, 97% ee). With the advantages of electrochemistry, excellent functional group tolerance and late-stage modification of complex natural products and pharmaceuticals made the established protocol greener and more economic. Mechanism investigation suggest that a NiI/NiIII cycle is involved in this electro-reductive reaction rather than metal reductant driven Ni0/NiII cycle. Overall, the efficient electrochemical activation and turnover of the nickel catalyst avoid the drawbacks posed by the employment of stoichiometric amount of sensitive metal powder reductants.

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Photoelectrochemical Asymmetric Catalysis Enables Enantioselective Heteroarylcyanation of Alkenes via C–H Functionalization

Cited by 32 publications

References 54 publications

Recent advances in catalytic asymmetric synthesis

Recent advances in catalytic asymmetric synthesis

Self‐ or Acridinium‐Catalyzed Electrophotosynthesis of Thiocyanato Heterocycles from Activated Alkenes

Electrochemically driven Nickel-Catalyzed Enantioselective Reductive Conjugate (Hetero)Arylation of Enones

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