Direct Access to α,β‐Unsaturated γ‐Lactams via Palladium‐Catalysed Carbonylation of Propargylic Ureas DOI Creative Commons

Debora Schiroli,

Aleksandr Voronov, Francesco Pancrazzi

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 4, 2024

Abstract Additive carbonylations typically necessitate strong nucleophiles, such as alcohols or amines. In this study, we carbonylated a poorly nucleophilic urea, under oxidant‐free conditions. Our straightforward carbonylative strategy enables access to versatile α,β‐unsaturated γ‐lactams featuring an aminocarbonyl fragment, utilizing readily available propargylic ureas starting materials. The employment of the PdI 2 /KI catalytic system allowed complete regioselectivity ( 5‐endo‐dig ), high functional group tolerance, broad substrate scope well operational simplicity (oxidant‐free, organic ligand‐free and base‐free protocol). synthetic utility these is showcased through late‐stage functionalizations, Giese reactions peptide couplings.

Language: Английский

Covalent Phenanthroline‐Porphyrin Polymer for Aminocarbonylation through Electro/Thermocatalytic Tandem Processes: Extending Chemical Valorization of CO2 DOI
Qing Li, Dong‐Dong Ma, Shenghua Zhou

et al.

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(25)

Published: Feb. 4, 2024

Abstract The covalent organic frameworks/polymers configurated with metal‐N 4 conjugated structures offer an exceptional platform for efficient electrochemical CO 2 reduction reaction (eCO RR). However, understanding the impact of structure‐mediated local microenvironment and integrating electroreduction follow‐up utilization toward extending chemical valorization are still far from sufficient. Herein, a set phenanthroline‐porphyrin polymers designed to decode modulation originating built‐in structures, optimized one delivered extraordinary performance eCO RR ≈100% Faradaic efficiency under stabilized ‐electrolysis 70 h. experimental theoretical analyses suggest that regulation Co‐N electronic convoys formation key intermediate * COOH. Furthermore, through CO‐mediated electro/thermocatalytic tandem processes, aminocarbonylation aryl iodides amines high yields has been convincingly implemented over coordinated Pd sites, which is remarkably helpful propel .

Language: Английский

Citations

6
Competing Mechanisms in Palladium-Catalyzed Alkoxycarbonylation of Styrene DOI Creative Commons
Jaya Mehara, Mariarosa Anania, Pavel Kočovský

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(8), P. 5710 - 5719

Published: April 1, 2024

Palladium-catalyzed carbonylation is a versatile method for the synthesis of various aldehydes, esters, lactones, or lactams. Alkoxycarbonylation alkenes with carbon monoxide and alcohol produces either saturated unsaturated esters as result two distinct catalytic cycles. The existing literature presents an inconsistent account procedures favoring oxidative products. In this study, we have monitored intermediates featured in both cycles methoxycarbonylation styrene PhCH=CH2 model substrate, including all short-lived intermediates, using mass spectrometry. Comparing reaction kinetics same mixture shows that proceeding via alkoxy intermediate [PdII]-OR, which gives rise to product PhCH=CHCO2Me, faster. However, advancing time, gradually changing conditions begin favor cycle dominated by palladium hydride [PdII]-H alkyl affording products PhCH2CH2CO2Me PhCH(CO2Me)CH3 preferentially. role oxidant proved be crucial: p-benzoquinone results gradual decrease pH during reaction, swaying system from toward cycle. By contrast, copper(II) acetate guards within 5-7 range facilitates formation complex favors producing PhCH=CHCO2Me high selectivity. Hence, it oxidant, rather than catalyst, controls outcome mechanistic switch. Unraveling these principles broadens scope developing alkoxycarbonylation reactions their application organic synthesis.

Language: Английский

Citations

5
Synthesis of Chiral Polycyclic Indoles via Pd(II)-Catalyzed Sequential Cyclization and Carbonylation DOI
Long Chen,

Hengrui Zhou,

Yiji Xue

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8739 - 8747

Published: May 21, 2024

Asymmetric tandem Heck and carbonylation reactions provide an efficient route to synthesize biologically important chiral cyclic compounds with a carbonyl group have attracted increasing research interests. However, this type of reaction relies on the initiation from oxidative addition aryl halides or pseudo halides, resulting in low atomic economy reaction. In addition, protocol has not adequately demonstrated reactivity generality heteroarene halides. Meanwhile, asymmetric Wacker-type cyclization are plagued by narrow substrate scope enantioselectivity remain underexplored. Herein, we describe Pd(II)-catalyzed sequential 1,6-enynes analogues carbon monoxide (CO). This catalytic system tolerates broad nucleophiles, including phenols, alcohols, amines. sequence forms four chemical bonds, two rings, up three stereocenters single step. strategy allows for convenient access variety polycyclic good yields enantio- diastereoselectivities, indoles, benzofurans, indole- benzofuran-fused bicyclo[3.2.1]octanes, indole-fused bicyclo[4.2.1]nonane.

Language: Английский

Citations

5
Synthesis of Sm‐TADDbBP@MCM‐41 as a Robust, Reusable, and Practical Nanocatalyst in the Homoselective [2 + 3] Cycloaddition Reaction DOI Open Access
Bahman Tahmasbi, Parisa Moradi, Fahimeh Mohammadi

et al.

Applied Organometallic Chemistry, Journal Year: 2024, Volume and Issue: 39(1)

Published: Oct. 16, 2024

ABSTRACT Schiff‐base materials are known ligands for the coordination of metal ions and synthesis various stable useful complexes. Therefore, herein, a novel compound {2,2′‐((1E,11E)‐2,5,8,11‐tetra azadodeca‐1,11‐diene‐1,12‐diyl) bis (4‐bromophenol)} was introduced that formed from condensation triethylenetetramine (TETA) 5‐bromo‐2‐hydroxybenzaldehyde (5B2HB). This ligand labeled as TADDbBP. Besides, mesoporous MCM‐41 synthesized using tetraethyl orthosilicate (TEOS), hydrolyzing cetyltrimethylammonium bromide (CTAB) NaOH solution (2 M), followed by calcination at 550 °C, further, silanol sites on MCM‐41's surface were modified 3‐chloropropyltriethoxysilane (3Cl‐PTES), which 3‐Cl‐Pr@MCM‐41. In next step, TADDbBP (as ligand) grafted 3‐Cl‐Pr@MCM‐41, TADDbBP@MCM‐41, it coordinated with samarium (which Sm‐TADDbBP@MCM‐41 nanocatalyst) Sm (CH 3 COO) . is first report production nanocatalyst, this nanocatalyst characterized TEM, SEM, EDX, elemental mapping, BET method, ICP, XRD, TGA techniques. final catalytic performance has been checked in homo‐selective producing tetrazoles through [2 + 3] cycloaddition benzonitriles sodium azide (NaN ) PEG‐400 available, nontoxic, green, safe solvent. provides excellent selectivity tetrazoles. addition, can be separated recycled several cycles without significant reactivation or leaching.

Language: Английский

Citations

4
Homo-Mannich Reaction of Cyclopropanols: A Versatile Tool for Natural Product Synthesis DOI
Tao Zhou, Qiuyuan Tan, Dan Jiang

et al.

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 17, 2025

ConspectusThe Mannich reaction, involving the nucleophilic addition of an enol(ate) intermediate to imine or iminium ion, is one most widely used synthetic methods for synthesis β-amino carbonyl compounds. Nevertheless, homo-Mannich which utilizes a homoenolate as partner and provides straightforward access valuable γ-amino compounds, remains underexplored. This can be largely attributed difficulties in generation manipulation species, despite various equivalents that have been developed. Among developed, cyclopropanol stands out due its intriguing reactivities endowed by highly strained cyclopropane. Upon activation metal, cyclopropyl alcohol prone undergo endocyclic C(sp3)–C(sp3) bond cleavage give β-keto radical intermediate, sets stage diverse range transformations. account outlines our recent progress development reaction applications natural product total synthesis. new methodology classified into two subtypes: 1) with imines ions 2) homo-Mannich-type heteroarenes. Through different ways generate ions, tandem sequential reactions C–H oxidation/homo-Mannich, Bischler–Napieralski/homo-Mannich, asymmetric allylation/homo-Mannich leading rapid assembly core scaffolds sarpagine, koumine, ibophyllidine, Aspidosperma, Melodinus, Kopsia alkaloids. Besides ring-opening indole pyrrole rings deliver schizozygane indolizidine Based on these advancements, we accomplished 29 alkaloids belonging 8 families. In this Account, present complete picture works concerning design, method development, It anticipated methodologies will find broad realm

Language: Английский

Citations

0
Highly efficient palladium-catalyzed carbonylation reactions of terpenes. DOI
Abdelouahd Oukhrib, Philippe Kalck, Martine Urrutigoı̈ty

et al.

Coordination Chemistry Reviews, Journal Year: 2025, Volume and Issue: 531, P. 216453 - 216453

Published: Feb. 12, 2025

Language: Английский

Citations

0
Regiodivergent Carbonylation of Alkenes: Selective Palladium‐Catalyzed Synthesis of Linear and Branched Selenoesters DOI Creative Commons

Zhusong Cao,

Qiang Wang, Helfried Neumann

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(2)

Published: Nov. 22, 2023

Abstract An unprecedented regiodivergent palladium‐catalyzed carbonylation of aromatic alkenes has been developed. Utilizing commercially available Pd(CH 3 CN) 2 Cl in the presence 1,1′‐ferrocenediyl‐bis( tert ‐butyl(pyridin‐2‐yl)phosphine) ligand L8 diverse selenoesters are obtained a straightforward manner. Key to success for control regioselectivity step is concentration acidic co‐catalyst. This general protocol features wide functional group compatibility and good regioselectivity. Mechanistic studies suggest that stoichiometric amounts acid changes properties coordination mode leading reversed

Language: Английский

Citations

9
Palladium catalysts supported on biodegradable urea-based polymers in synthesis with CO – part B DOI
Martin Markovič, Pavol Lopatka, Peter Koóš

et al.

Catalysis Today, Journal Year: 2024, Volume and Issue: 440, P. 114831 - 114831

Published: May 24, 2024

Language: Английский

Citations

3
Gold‐Catalyzed Alkoxy‐Carbonylation of Aryl and Vinyl Iodides DOI
Vivek W. Bhoyare, Asish Bera, Vincent Gandon

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: July 23, 2024

Abstract Herein, for the first time, we disclose gold‐catalyzed alkoxy‐carbonylation of aryl and vinyl iodides utilizing ligand‐enabled Au(I)/Au(III) redox catalysis. The present methodology is found to be general, efficient, employs mild reaction conditions showcases a broad substrate scope even with structurally complex molecules. Density functional theory (DFT) calculations revealed mechanistic pathways distinct from those conventional transition metal‐catalyzed carbonylation reactions.

Language: Английский

Citations

3
Fe3O4@SiO2-DHB/DI(S-NH)-Pd(0) nanocomposite: a novel, efficient, and reusable heterogeneous catalyst for carbonylative preparation of N-aryl amides DOI Creative Commons
Ahmed M. H. Abudken, Lina Saadi, Rehan Ali

et al.

BMC Chemistry, Journal Year: 2025, Volume and Issue: 19(1)

Published: March 15, 2025

N-aryl amides hold significant importance in organic chemistry due to their widespread presence pharmaceuticals, agrochemicals, and various bioactive compounds. As a result, catalysts preparation methodologies for amide derivatives have long been target of active investigation interest. In the current work, simple accessible route was adopted magnetic catalyst [Fe3O4@SiO2-DHB/DI(S-NH)-Pd (0)] then its catalysis three-component synthesis via carbonylation reaction between aryl iodides amines examined. experiments, efficiency producing range with high yields short under mild conditions unequivocally confirmed, confirmed through experiments. High desired compound ease separation, reusability catalysts, conditions, accommodation substrates, thorough analysis determination produced compounds characterization purification taken as key features this work.

Language: Английский

Citations

0