Copper-catalysed radical reactions of alkenes, alkynes and cyclopropanes with N–F reagents

Muñoz‐Molina, José María; Belderraín, Tomás R.; Pérez, Pedro J.

doi:10.1039/d0ob01743d

Cited by 17 publications

(9 citation statements)

References 58 publications

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“…Then trifluoromethylation provides products 3.5.43 with the reverse regioselectivity (Scheme 206). 464 Li, Zhu, and co-workers have developed an unprecedented protocol for aminotrifluoromethylation reaction of both activated and unactivated alkenes which is driven by N-centered radical addition to the double bond. 465 According to this protocol, when alkenes were treated with 10 mol % Cu(OTf) 2 as the catalyst, (bpy)Zn(CF 3 ) 2 (1.5 equiv) as the CF 3 − source, in the presence of Zn(OTf) 2 (50 mol %) and Zn(OAc) 2 (50 mol %) as additives together with N-fluorobis(benzenesulfonyl)imide (NFSI: source of bis sulfonimidyl radical) at room temperature for 12−24 h, the expected aminotrifluoromethylation products were obtained in satisfactory yields with high Liu and Lin also developed the copper-catalyzed enantioselective aminocyanation reaction of styrenes using NFSI as the imidyl radical precursor via reaction with Cu(I) catalyst.…”

Section: Cascade Involving Addition To Alkenesmentioning

confidence: 99%

Enantioselective Radical Reactions Using Chiral Catalysts

Mondal¹,

et al. 2022

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Scheme 24 Enantioselective Radical Hydroacylation of Enals with α-Ketoacids byMerging Photoredox Catalysis with Amine Catalysis.Jang et al. exploited enantioselective tandem Michael addition/oxyamination of α,β-unsaturated aldehydes by combining asymmetric iminium catalysis using organocatalyst with photoinduced SOMO catalysis using N719/TiO2. 60 Here, TiO2 acts as a second cooperative photocatalyst along with Ru photocatalyst N719 which bound to the latter, increases the enantio-and diastereoselectivity of the process. Adamantane carboxylic acid (30 mol%) was used as an additive which promotes formation of iminium ion 2.1.48A from aldehyde 2.1.48 and chiral amine catalyst. This iminium intermediate then reacts with diethyl malonate to provide intermediate 2.1.48B which either undergoes hydrolysis to form β-substituted aldehyde 2.1.50 or photo-oxidation by the photoexcited Ru(II) dye to form enamine radical 2.1.48C. Subsequent addition of TEMPO to radical intermediate 2.1.48BC followed by hydrolysis afforded the desired product 2.1.49 (Scheme 25). This mechanism is obeying to a polar/radical crossover sequence where the first stereocontrol arises from the addition of the malonate.Recently, Bach group reported promising preliminary results of enantioselective [2+2] photocycloaddition of cinnamaldehyde in the presence of ruthenium photocatalyst and proline derived organocatalyst. 61

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Section: Cascade Involving Addition To Alkenesmentioning

confidence: 99%

Enantioselective Radical Reactions Using Chiral Catalysts

Mondal¹,

et al. 2022

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“…Despite the intrinsic potential to impart both, relative and absolute stereocontrol in the newly formed stereocenters 17 , asymmetric variants of these transformations, especially in intermolecular settings, are extremely scarce. Among the reported polar [18][19][20][21] and radical [22][23][24][25][26][27][28][29] mediated processes, only a handful of examples capitalizing on styrene derivatives as starting materials enabled the synthesis of optically pure β,β-diarylethylamines. Seminal work by Hajra et al showcased a two-electron Cu-catalyzed olefin aziridination/intramolecular Friedel-Craft reaction to produce trans-2-aminoaryltetralins in up to 96:4 e.r.…”

Section: Introductionmentioning

confidence: 99%

Chiral arylsulfinylamides: all-in-one reagents for visible light-mediated asymmetric alkene aminoarylations

Hervieu

Kirillova

et al. 2022

Preprint

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Two- or one-electron mediated alkene aminoarylations represent straightforward approaches to assemble molecular complexity by the simultaneous formation of two contiguous Csp3-Csp2/Csp3-N stereocenters. While racemic versions have been extensively explored, asymmetric variants, especially those involving open-shell C-centered radical species, are much more limited both in number and scope. In this work, we describe enantioenriched arylsulfinylamides as all-in-one reagents for the efficient asymmetric, intermolecular aminoarylation of alkenes. Under mild photoredox conditions, Nitrogen addition of the arylsulfinylamide onto the double bond followed by 1,4-translocation of the aromatic ring produce the corresponding aminoarylation adducts in a single operation. The sulfinyl group acts here as a traceless chiral auxiliary and is eliminated in situ under the reaction conditions. Optically pure beta, beta-diarylethyl- and aryl-alpha, beta-ethylenediamines, prominent motifs in pharmaceuticals and bioactive natural products, are obtained with excellent levels of regio-, relative and absolute stereocontrol.

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“…Copper-catalyzed reactions of alkynes have advanced significantly over the past few decades, and several useful reviews have been published on the chemistry of alkynes with copper metal. [33][34][35][36][37][38][39] In recent years, studies have been carried out on catalysts based on mesoporous materials doped with rare earth elements (REEs). In studies devoted to the influence of the promoting activity of various nature metals, in particular, when comparing the activity of REEs and d-elements, it was found that the catalyst doped with REE had the best performance.…”

Section: Introductionmentioning

confidence: 99%

“…The reason for the preferred use of copper lies in its low cost, non‐toxicity, and easy availability. Copper‐catalyzed reactions of alkynes have advanced significantly over the past few decades, and several useful reviews have been published on the chemistry of alkynes with copper metal 33–39 …”

Section: Introductionmentioning

confidence: 99%

Mesoporous silica gel doped with dysprosium and modified with copper: A selective catalyst for the hydrogenation of 1‐hexyne/1‐hexene mixture

Tokranova

Tokranov

Vinogradov

et al. 2022

Int J of Chemical Kinetics

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The selective hydrogenation of 1-hexyne/1-hexene mixture in the temperature range 100-140 • C and a hydrogen pressure of 3 atm was studied on catalysts based on mesoporous silica gel modified with copper and mesoporous silica gel doped with dysprosium and modified with copper. The physicochemical characteristics of the samples were studied by low temperature nitrogen adsorption-desorption method, scanning electron microscopy (SEM), X-ray fluorescence (XRF), and inductively coupled plasma mass spectrometry (ICP-MS). In addition, theoretical calculations of the entropies and energies of formation of activated complexes of the hydrogenation reactions of 1-hexyne and 1-hexene in the gas phase have been calculated with Gaussian 09 software using the density functional theory (DFT) B3LYP/cc-pVQZ method. It was found that the presence of dysprosium in the structure of mesoporous silica gel leads to an increase in catalytic activity in the hydrogenation of 1-hexyne. Moreover, it was shown that mesoporous silica gel modified with copper has the highest selectivity for hexene-1 in the hydrogenation reaction of 1-hexyne/1-hexene mixture at 130 • C.

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Copper-catalysed radical reactions of alkenes, alkynes and cyclopropanes with N–F reagents

Abstract: The mild generation of nitrogen-centred radicals from N-F reagents has become a convenient synthetic tool. This methodology provides access to the aminative difunctionalisation of alkenes and alkynes, and the radical...

Cited by 17 publications

References 58 publications

Enantioselective Radical Reactions Using Chiral Catalysts

Enantioselective Radical Reactions Using Chiral Catalysts

Chiral arylsulfinylamides: all-in-one reagents for visible light-mediated asymmetric alkene aminoarylations

Mesoporous silica gel doped with dysprosium and modified with copper: A selective catalyst for the hydrogenation of 1‐hexyne/1‐hexene mixture

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