Visible-light-induced triple catalysis for a ring-opening cyanation of cyclopropyl ketones

Liu, Jing; Liu, Xiaopeng; Wu, Hai‐Yin; Yi, Wei; Lu, Fu‐Dong; Guo, Kai-Rui; Cheng, Ying; Xiao, Wen‐Jing

doi:10.1039/d0cc05167e

Cited by 28 publications

(31 citation statements)

References 45 publications

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“…Ring-opening of cyclopropyl ketones followed by cyanation for the synthesis of γ-cyano ketones. [73] expected product, probably due to less effectiveness in the ring-opening step.…”

Section: Reactions Involving Acyl Cyclopropanesmentioning

confidence: 97%

“…In 2020, Xiao et al reported the visible light-induced ringopening reaction of cyclopropyl ketones 9 followed by cyanation for the synthesis of γ-cyano ketones 29 (Scheme 20). [73] For the first time, a synergistic triple catalyst system of photocatalyst, Lewis acid and copper catalyst is used in the selective cleavage of cyclopropane ring. Ph-PTZ was employed as the photocatalyst along with lanthanum (III) triflate as the Lewis acid catalyst and Cu(MeCN) 4 BF 4 complex.…”

Section: Reactions Involving Acyl Cyclopropanesmentioning

confidence: 99%

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Visible‐Light‐Mediated Ring‐Opening Reactions of Cyclopropanes

et al. 2021

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Dedicated to Professor Ibrahim Ibnusaud for his outstanding contributions in the field of organic synthesisDue to the high reactivity of cyclopropanes, different methods have been developed for their stereo-and regio-controlled ring-opening reactions to achieve a variety of synthetically useful targets. The traditional methods for the ring-opening include thermolysis, use of oxidants, transition metals or radical precursors in which many of them encounter various difficulties. In the past several years, visible-light-mediated photoredox reactions received considerable attention for various organic transformations. Several methodologies have been developed in recent times for the visible-light-mediated ring-opening reactions of cyclopropanes. Considering the synthetic potential of this class of reactions, we provide a summary of various methodologies developed for the cyclopropane ring-opening reactions under visible-light photoredox catalysis.

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“…Ring-opening of cyclopropyl ketones followed by cyanation for the synthesis of γ-cyano ketones. [73] expected product, probably due to less effectiveness in the ring-opening step.…”

Section: Reactions Involving Acyl Cyclopropanesmentioning

confidence: 97%

Section: Reactions Involving Acyl Cyclopropanesmentioning

confidence: 99%

Visible‐Light‐Mediated Ring‐Opening Reactions of Cyclopropanes

et al. 2021

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“…The reaction with cyclopropane acyl imidazoles furnished the respective ketone products (3 i,j) in good yields, an unexpected result that provides additional mechanistic insight into the nature of III. Compared to traditional acyl radicals, which have demonstrated radical clock-like reactivity, [29] the distribution of radical density between C1 and C2 affords increased stability, thus illustrating a significant advantage of NHC-based radical chemistry. The chemoselectivity of this process was demonstrated in the isolation of ester-containing 3 k, illustrating a bond construction that suffers from functional group incompatibility using conventional methods of ketone formation (e.g., Grignard reaction, see Supporting Information, page S17).…”

Section: Angewandte Chemiementioning

confidence: 99%

Light‐Driven Carbene Catalysis for the Synthesis of Aliphatic and α‐Amino Ketones

et al. 2021

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Single‐electron N‐heterocyclic carbene (NHC) catalysis has gained attention recently for the synthesis of C−C bonds. Guided by density functional theory and mechanistic analyses, we report the light‐driven synthesis of aliphatic and α‐amino ketones using single‐electron NHC operators. Computational and experimental results reveal that the reactivity of the key radical intermediate is substrate‐dependent and can be modulated through steric and electronic parameters of the NHC. Catalyst potential is harnessed in the visible‐light driven generation of an acyl azolium radical species that undergoes selective coupling with various radical partners to afford diverse ketone products. This methodology is showcased in the direct late‐stage functionalization of amino acids and pharmaceutical compounds, highlighting the utility of single‐electron NHC operators.

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“…47 Moreover, when treated sequentially with Raney-Ni under a H2 atmosphere and tosyl chloride (TsCl), α-ketoamide 3aq could undergo intramolecular reductive amination to give Ts-protected piperidine derivatives 9a and 9b respectively with moderate isolated yields. 48 Notably, by combining acid-promoted condensation with N-phenyl hydrazine and Lewis acid-mediated Fischer indolization process in a one-pot manner, 3aq was easily converted into 2,3-disubstituted indole 10 in 71% yield. 49 Interestingly, Pd-catalyzed cascade reaction of 3aq with arylboronic acid enabled synthesis of valuable 2,6-disubstituted pyridine 11 in 85% yield.…”

Section: Synthetic Applicationsmentioning

confidence: 99%

Switchable radical carbonylation by polarity-regulation

Lü

Xiao

et al. 2021

Preprint

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Carbonylation reactions involving CO as readily available C1 synthons have become one of the most important tools for construction of carbonyl compounds from feedstock chemicals in modern chemical synthesis. Whereas numerous catalytic methods for carbonylation reactions proceeding via ionic or radical pathways have been reported, an inherent limitation to these methods is the need to control switchable single and double carbonylative formation of value-added products from the same and simple starting materials. Here we describe a new strategy that exploits simple visible-light-driven photoredox catalysis to regulate the polarity of coupling partners to drive switchable radical carbonylation reactions. Controlled trap of various alkyl radicals by single or double CO thereby proceed smoothly with excellent selectivity in the presence of various amine nucleophiles at room temperature, generating valuable amides and α-ketoamides in a versatile and controlled fashion. Combined experimental and DFT computational studies suggest that trap of the initially formed acyl radical by the second molecule of CO to form α-ketoacyl radical is a facile but reversible process; and photoredox-catalyzed SET oxidation of natural nucleophilic amines into relatively electrophilic nitrogen radical cations is responsible for switchable coupling with such two radical intermediates.

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Visible-light-induced triple catalysis for a ring-opening cyanation of cyclopropyl ketones

Abstract: An unprecedented triple catalytic, general ring-opening cyanation reaction of cyclopropyl ketones to construct γ-cyanoketones is described. The key is to merge photoredox catalysis with Lewis acid catalysis and copper catalysis...

Cited by 28 publications

References 45 publications

Visible‐Light‐Mediated Ring‐Opening Reactions of Cyclopropanes

Visible‐Light‐Mediated Ring‐Opening Reactions of Cyclopropanes

Light‐Driven Carbene Catalysis for the Synthesis of Aliphatic and α‐Amino Ketones

Switchable radical carbonylation by polarity-regulation

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