Emergence of Copper‐Mediated Formation of C–C Bonds

Maaliki, Carine; Thiery, Emilie; Thibonnet, J.

doi:10.1002/ejoc.201600540

Cited by 62 publications

(21 citation statements)

References 206 publications

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“…The retrosynthesis of 16-F 1t -, 16-E 1 -and 16-D 1t -PhytoPs 1-3 is based on common precursor 4, which can be easily transformed to all target compounds by simple deprotection, protection and oxidation reactions (Scheme 2). This orthogonally protected PhytoP structure 4 was envisaged to be obtained by copper(I)-catalyzed C(sp 3 )-C(sp 3 ) coupling 49 oxidative radical anion cyclization using ferrocenium hexafluorophosphate 6 and the stable radical 2,2,6,6-tetramethylpiperidine N-oxyl (TEMPO) 7 paves the way for construction of the central cyclic structure 5. Cyclization substrate 8 should be easily prepared from commercially available (E,E)-2,4-heptadienal (9) and methyl acetoacetate (10).…”

Section: Resultsmentioning

confidence: 99%

Total syntheses of all tri-oxygenated 16-phytoprostane classes via a common precursor constructed by oxidative cyclization and alkyl–alkyl coupling reactions as the key steps

2017

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A unified strategy for the total synthesis of the methyl esters of all phytoprostane (PhytoP) classes bearing two ring-oxygen atoms based on an orthogonally protected common precursor is described. Racemic 16-F-, 16-E-PhytoP and their C-16 epimers, which also occur as racemates in Nature, were successfully obtained. The first total synthesis of very sensitive 16-D-PhytoP succeeded, however, it quickly isomerized to more stable, but so far also unknown Δ-16-D-PhytoP, which may serve as a more reliable biomarker for D-type PhytoP. The dioxygenated cyclopentane ring carrying the ω-chain with the oxygen functionality in the 16-position was approached by a radical oxidative cyclization mediated by ferrocenium hexafluorophosphate and TEMPO. The α-chain was introduced by a new copper-catalyzed alkyl-alkyl coupling of a 6-heptenyl Grignard reagent with a functionalized cyclopentylmethyl triflate.

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Section: Resultsmentioning

confidence: 99%

Total syntheses of all tri-oxygenated 16-phytoprostane classes via a common precursor constructed by oxidative cyclization and alkyl–alkyl coupling reactions as the key steps

2017

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“…Two-dimensional transition-metal chalcogenides have tremendously impacted the areas of heterogeneous catalysis in many organic transformation reactions, such as in oxidation, reduction, C-C coupling, C-S coupling, C-N coupling, etc. Crosscoupling (C-C) reactions play the main role in organic synthesis to set up the carbon skeleton of organic molecules (Maaliki et al, 2017). Transition-metal based catalysts (such as Pd, Cu, Ni etc.)…”

Section: Introductionmentioning

confidence: 99%

Hydrothermally Synthesized CuCo2S4 Nanosheets as an Easily Accessible and Convenient Heterogeneous Catalyst for the Sonogashira Cross-Coupling Reactions

2019

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A high surface area and the possibility of high charge separation and transportability make the two-dimensional (2D) nanomaterials very special in many applications, particularly in the field of catalysis. The usefulness of 2D nanomaterial is positively demonstrated in this study by employing it as an efficient heterogeneous catalyst in Sonogashira cross-coupling reaction, where the later one is well known for the formation of carbon-carbon bonds. 2D nanosheets of CuCo 2 S 4 are synthesized using a hydrothermal synthesis and the average thickness of the sheets is found to be in the range of 10-15 nm. The transparent nanosheets are interconnected to form thick sheets and then aggregated to form a highly open three-dimensional hierarchical structure. This study explores the Sonogashira reaction very efficiently in water/ethanol at room temperature using hydrothermally synthesized CuCo 2 S 4 nanosheets as catalyst for the CC coupling reaction for the first time. The developed method is found to be economic, green, high yields, low catalyst loading and reusability of the catalysts. This present CuCo 2 S 4 nanosheet heterogeneous catalyst afford the Sonogashira coupling of various aryl halides with terminal alkynes, giving a variety of aryl acetylenes in excellent yields and can be recovered by a simple filtration and reused for at least 10 consecutive reactions with almost constant yield and activity.

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“…Among the series of organometallic catalysis reactions, copper catalysis has offered an inexpensive, environmentally friendly alternative to the use of precious metals [25][26][27][28][29][30][31][32][33][34]. Shibasaki et al described a possible solution to a catalytic enantioselective allylation of ketoimines.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Calculations on the Mechanism of Enantioselective Copper(I)-Catalyzed Addition of Enynes to Ketones

Tao

Qin

2018

Catalysts

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Computational investigations on the bisphospholanoethane (BPE)-ligated Cu-catalyzed enantioselective addition of enynes to ketones were performed with the density functional theory (DFT) method. Two BPE-mesitylcopper (CuMes) catalysts, BPE-CuMes and (S,S)-Ph-BPE–CuMes, were employed to probe the reaction mechanism with the emphasis on stereoselectivity. The calculations on the BPE-CuMes system indicate that the active metallized enyne intermediate acts as the catalyst for the catalytic cycle. The catalytic cycle involves two steps: (1) ketone addition to the alkene moiety of the metallized enyne; and (2) metallization of the enyne followed by the release of product with the recovery of the active metallized enyne intermediate. The first step accounts for the distribution of the products, and therefore is the stereo-controlling step in chiral systems. In the chiral (S,S)-Ph-BPE–CuMes system, the steric hindrance is vital for the distribution of products and responsible for the stereoselectivity of this reaction. The steric hindrance between the phenyl ring of the two substrates and groups at the chiral centers in the ligand skeleton is identified as the original of the stereoselectivity for the titled reaction.

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Emergence of Copper‐Mediated Formation of C–C Bonds

Cited by 62 publications

References 206 publications

Total syntheses of all tri-oxygenated 16-phytoprostane classes via a common precursor constructed by oxidative cyclization and alkyl–alkyl coupling reactions as the key steps

Total syntheses of all tri-oxygenated 16-phytoprostane classes via a common precursor constructed by oxidative cyclization and alkyl–alkyl coupling reactions as the key steps

Hydrothermally Synthesized CuCo2S4 Nanosheets as an Easily Accessible and Convenient Heterogeneous Catalyst for the Sonogashira Cross-Coupling Reactions

Theoretical Calculations on the Mechanism of Enantioselective Copper(I)-Catalyzed Addition of Enynes to Ketones

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