Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents

Chemical Reviews, Год журнала: 2024, Номер unknown

Опубликована: Сен. 13, 2024

Hypervalent iodine(III) compounds have found wide application in modern organic chemistry as environmentally friendly reagents and catalysts. iodine are commonly used synthetically important halogenations, oxidations, aminations, heterocyclizations, various oxidative functionalizations of substrates. Iodonium salts arylating reagents, while iodonium ylides imides excellent carbene nitrene precursors. Various derivatives benziodoxoles, such azidobenziodoxoles, trifluoromethylbenziodoxoles, alkynylbenziodoxoles, alkenylbenziodoxoles group transfer the presence transition metal catalysts, under metal-free conditions, or using photocatalysts photoirradiation conditions. Development hypervalent catalytic systems discovery highly enantioselective reactions chiral represent a particularly recent achievement field chemistry. Chemical transformations promoted by many cases unique cannot be performed any other common, non-iodine-based reagent. This review covers literature published mainly last 7-8 years, between 2016 2024.

Язык: Английский

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Iron^III-catalyzed asymmetric inverse-electron-demand hetero-Diels–Alder reaction of dioxopyrrolidines with simple olefins

Chemical Science, Год журнала: 2024, Номер 15(13), С. 4797 - 4803

Опубликована: Янв. 1, 2024

A highly enantioselective [4 + 2] cycloaddition of a number simple olefins with cyclic hetero-diene dioxopyrrolidines is realized by chiral iron( iii )/ N , ′-dioxide complex catalyst.

Язык: Английский

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Nickel-Catalyzed Hydrofluorination in Unactivated Alkenes: Regio- and Enantioselective C–F Bond Formation

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(13), С. 9375 - 9384

Опубликована: Март 21, 2024

Catalytic formation of a regio- and enantioselective C–F bond chiral center from readily available alkenes is crucial goal, yet it continues to pose significant challenges in organic synthesis. Here, we report the regioselective bonds facilitated by NiH catalysis coordination directing strategy that enables precise hydrofluorination both terminal internal alkenes. Notably, have optimized this methodology achieve high enantioselectivity creating aliphatic stereogenic centers especially with β,γ-alkenyl substrates, using tailored Bn-BOx ligand. Another pivotal finding our research identification (+)-nonlinear effect under conditions, allowing for even moderately enantiomerically enriched ligands. Given role fluorine pharmaceuticals synthetic materials, offers essential insights into centers, paving way efficient production valuable fluorinated compounds.

Язык: Английский

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Iron-Catalyzed Asymmetric Imidation of Sulfides via Sterically Biased Nitrene Transfer

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(26), С. 18050 - 18060

Опубликована: Июнь 15, 2024

Transition-metal-catalyzed enantioselective nitrene transfer to sulfides has emerged as one of the most powerful strategies for rapid construction enantioenriched sulfimides. However, achieving stereocontrol over highly active earth-abundant transition-metal nitrenoid intermediates remains a formidable challenge compared with precious metals. Herein, we disclose chiral iron(II)/N,N′-dioxide-catalyzed imidation dialkyl and alkyl aryl using iminoiodinanes precursors. A series sulfimides were obtained in moderate-to-good yields high enantioselectivities (56 examples, up 99% yield, 98:2 e.r.). The utility this methodology was demonstrated by late-stage modification complex molecules synthesis insecticide sulfoxaflor related bioactive compounds. Based on experimental studies theoretical calculations, water-bonded high-spin iron species identified key intermediate. observed stereoselectivity original from steric repulsion between amide unit ligand cave bulky substituent sulfides. Additionally, dioxazolones proved be suitable acylnitrene precursors presence an iron(III)/N,N′-dioxide complex, resulting formation enantioselectivity-reversed (14 81% 97:3

Язык: Английский

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A Core-Shell Confinement Strategy Towards Single-Atom Fe-N/S-C Bifunctional Catalyst for Selective Nitroarene Reduction and Olefin Epoxidation

Journal of Alloys and Compounds, Год журнала: 2025, Номер 1012, С. 178488 - 178488

Опубликована: Янв. 1, 2025

Язык: Английский

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Data Science Guided Multiobjective Optimization of a Stereoconvergent Nickel-Catalyzed Reduction of Enol Tosylates to Access Trisubstituted Alkenes

ACS Catalysis, Год журнала: 2024, Номер 14(7), С. 4699 - 4708

Опубликована: Март 13, 2024

Herein we report a method for stereoconvergent synthesis of trisubstituted alkenes in two steps from simple ketone starting materials. The key step is nickel-catalyzed reduction the corresponding enol tosylates that predominantly relies on monophosphine ligand to direct formation either E- or Z-trisubstituted alkene products. Reaction optimization was accomplished using data science workflow including training set design, statistical modeling, and multiobjective Bayesian optimization. campaign significantly improved access both products up ∼90:10 diastereoselectivity >90% yield. After identifying superior ligands only 25 reactions were required each objective (E- Z-isomer formation) converge reaction parameters search space ∼30,000 potential conditions EDBO+ platform. Additionally, hierarchical machine learning model developed predict stereoselectivity untested achieve validation mean absolute error (MAE) 7.1% selectivity (0.21 kcal/mol). Ultimately, present synergistic leveraging integration optimization, thereby expanding stereodefined alkenes.

Язык: Английский

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Bipyridine-N,N′-dioxides Catalysts: Design, Synthesis, and Application in Asymmetric Synthesis of 1H-Pyrazolo[3,4-b]pyridine Analogues

Organic Letters, Год журнала: 2024, Номер 26(17), С. 3487 - 3492

Опубликована: Апрель 18, 2024

A novel type of highly efficient chiral C2-symmetric bipyridine-N,N′-dioxides ligand application in catalyzing Michael addition/Cyclization 5-aminopyrazoles with α,β-unsaturated 2-acyl imidazoles has been developed, affording the corresponding adducts 85–97% yield up to 99% enantioselectivity under mild conditions a lower catalyst loading and broad scope. Remarkably, this protocol exhibits advantages terms reactivity enantioselectivity, giving fact that as low 2.2 mol % L1 2.0 Ni(OTf)2 can promote title reaction on gram scale afford desired product excellent enantioselectivity.

Язык: Английский

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Advancing Heterogeneous Organic Synthesis With Coordination Chemistry‐Empowered Single‐Atom Catalysts

Advanced Materials, Год журнала: 2024, Номер unknown

Опубликована: Сен. 18, 2024

Abstract For traditional metal complexes, intricate chemistry is required to acquire appropriate ligands for controlling the electron and steric hindrance of active centers. Comparatively, preparation single‐atom catalysts much easier with more straightforward effective accesses arrangement control The presence coordination atoms or neighboring functional on supports' surface ensures stability single‐atoms their interactions individual substantially regulate performance Therefore, collaborative interaction between surrounding environment enhances initiation reaction substrates formation transformation crucial intermediate compounds, which imparts significant catalytic efficacy, rendering them a valuable framework investigating correlation structure activity, as well mechanism in organic reactions. Herein, comprehensive overviews both homogeneous complexes reactions are provided. Additionally, reflective conjectures about advancement synthesis also proposed present reference later development.

Язык: Английский

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Chiral Lewis Acid-Catalyzed Asymmetric Multicomponent Michael Reaction through [1,2]-Phospha-Brook Rearrangement

Organic Letters, Год журнала: 2023, Номер 25(34), С. 6262 - 6266

Опубликована: Авг. 21, 2023

The multicomponent catalytic asymmetric Pudovik addition/[1,2]-phospha-Brook rearrangement/Michael reaction sequence of isatins, phosphites, and 4-oxobutenoates was realized. A series oxindole derivatives containing two contiguous stereocenters obtained in high yields excellent stereoselectivities (up to >99% yield, >95:5 dr, ee) using a chiral Lewis acid catalyst. possible model is presented illustrate the stereocontrol.

Язык: Английский

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A non-heme diiron monooxygenase PmlABCDEF enables access to selective oxidation of O-alkenyl substituted pyridines

Molecular Catalysis, Год журнала: 2025, Номер 574, С. 114866 - 114866

Опубликована: Янв. 31, 2025

Язык: Английский

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