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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Tertiary Amides as Directing Groups for Enantioselective C−H Amination using Ion‐Paired Rhodium Complexes

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(14)

Опубликована: Фев. 13, 2024

Abstract Enantioselective C−H amination at a benzylic methylene is vital disconnection towards chiral benzylamines. Here we disclose that butyric and valeric acid‐derived tertiary amides can undergo highly enantioselective using an achiral anionic Rh complex ion‐paired with Cinchona alkaloid‐derived cation. A broad scope of compounds be aminated encompassing numerous arene substitutions, amides, two different chain lengths. Excellent tolerance ortho substituents was observed, which has not been achieved before in asymmetric intermolecular Rh. We speculate the amide group substrate engages hydrogen bonding interactions directly cation, enabling high level organisation transition state for amination. This contrast our previous work where bearing bond donor required. Control experiments led to discovery methyl ethers also function as proficient directing groups under optimised conditions, potentially acting acceptors. finding promise dramatically expand applicability catalysts.

Язык: Английский

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Intermolecular Enantioselective Amination Reactions Mediated by Visible Light and a Chiral Iron Porphyrin Complex

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(34)

Опубликована: Май 2, 2024

In the presence of 1 mol % a chiral iron porphyrin catalyst, various 3-arylmethyl-substituted 2-quinolones and 2-pyridones underwent an enantioselective amination reaction (20 examples; 93-99 ee). The substrates were used as limiting reagents, fluorinated aryl azides (1.5 equivalents) served nitrene precursors. is triggered by visible light which allows facile dediazotation at ambient temperature. selectivity governed two-point hydrogen bond interaction between ligand catalyst substrate. Hydrogen bonding directs to specific atom within substrate that displaced nitrogen substituent either in concerted fashion or rebound mechanism.

Язык: Английский

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Skeletal Editing by Hypervalent Iodine Mediated Nitrogen Insertion

Chemistry - A European Journal, Год журнала: 2024, Номер unknown

Опубликована: Июль 24, 2024

Hypervalent iodine reagents are versatile and readily accessible that have been extensively applied in contemporary synthesis modern organic chemistry. Among them, iodonitrene (ArI=NR), is a powerful reactive species, widely used for single-nitrogen-atom insertion reaction, skeletal editing to construct N-heterocycles. Skeletal with components has recently emerged as an exciting approach chemical transformation. These produce biologically relevant heterocycles functionalized molecular architectures. Recently, the of nitrogen-atom into hydrocarbons generate N-heterocyclic compounds using hypervalent significant focus field reactions. In this review, we discuss rapidly emerging nitrene insertion, including nitrogen access nitrogen-containing heterocycles, current mechanistic understanding these processes.

Язык: Английский

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Biocatalytic Synthesis of α-Amino Esters via Nitrene C–H Insertion

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(40), С. 27267 - 27273

Опубликована: Сен. 27, 2024

α-Amino esters are precursors to noncanonical amino acids used in developing small-molecule therapeutics, biologics, and tools chemical biology. α-C-H amination of abundant inexpensive carboxylic acid through nitrene transfer presents a direct approach α-amino esters. Methods for nitrene-mediated the protic bonds esters, however, underdeveloped. This gap arises because hydrogen atom abstraction (HAA) C-H by electrophilic metal-nitrenoids is slow: preferentially react with polarity-matched, hydridic bonds, even when weaker present. study describes discovery evolution highly stable protoglobin transferases that catalyze enantioselective intermolecular We developed high-throughput assay evaluate activity enantioselectivity mutant enzymes together their sequences using Every Variant Sequencing (evSeq) method. The enabled identification enantiodivergent function at ambient conditions

Язык: Английский

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Design Approaches That Utilize Ionic Interactions to Control Selectivity in Transition Metal Catalysis

Chemical Reviews, Год журнала: 2025, Номер unknown

Опубликована: Фев. 28, 2025

The attractive force between two oppositely charged ions can constitute a powerful design tool in selective catalysis. Enzymes make extensive use of ionic interactions alongside variety other noncovalent interactions; recent years have seen synthetic chemists begin to seriously explore these catalyst designs that also incorporate reactive transition metal. In isolation, single interaction exhibits low directionality, but many successful systems they exist additional which provide high degree organization at the selectivity-determining state. Even situations with key interaction, directionality is not always detrimental, and even be advantageous, conferring generality catalyst. This Review explores approaches utilize control selectivity metal It divided into halves: first, occurs outer sphere complex, using ligand or bound an anion; second, bears formal charge, associated counterion.

Язык: Английский

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Nitrene-mediated Aminative N–N–N Coupling: Facile Access to Triazene 1-Oxides

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

A nitrene-mediated aminative N–N–N coupling enables direct triazene 1-oxide synthesis via an aminonitrene–nitrosoarene pathway.

Язык: Английский

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Decomposition and sintering behaviors of MOD-assisted Ag pastes for power electronics

Materials Today Communications, Год журнала: 2025, Номер unknown, С. 112265 - 112265

Опубликована: Март 1, 2025

Язык: Английский

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Enantioselective palladium-catalyzed α-arylation of primary alkylamines

Chem Catalysis, Год журнала: 2025, Номер unknown, С. 101331 - 101331

Опубликована: Март 1, 2025

Язык: Английский

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Catalytic Metalloradical System for Radical 1,6-C(sp³)–H Amination with Concurrent Control of Site-, Chemo-, and Enantio-selectivity

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 22, 2025

A catalytic radical process has been developed via metalloradical catalysis (MRC) for 1,6-C(sp3)-H amination with concurrent control of site-, chemo-, and enantioselectivity. Supported by an optimal D2-symmetric chiral amidoporphyrin ligand, the Co(II)-based system effectively catalyzes chemoselective propargylic, allylic, benzylic C-H bonds at 1,6- over 1,5-positions alkoxysulfonyl azides, achieving high This Co(II)-catalyzed process, which operates room temperature, is applicable to a broad range azides tolerance functional groups, enabling efficient construction six-membered sulfamidates in yields excellent enantioselectivities. Comprehensive experimental investigations, complemented computational studies, elucidate stepwise mechanism underlying this transformation. The resulting cyclic from enantioselective can undergo stereospecific ring-opening reactions various nucleophiles, affording γ-functionalized α-chiral amines while retaining original enantiopurity. Since are readily synthesized widely available alcohols through nucleophilic azide transfer, union ionic processes constitutes versatile 1,3-difunctionalization alcohols.

Язык: Английский

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