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

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(26), P. 18050 - 18060

Published: June 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

Language: Английский

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Nitrene-mediated glycosylation with thioglycoside donors under metal catalysis

Science Advances, Journal Year: 2025, Volume and Issue: 11(8)

Published: Feb. 21, 2025

Glycosylation chemistry plays a pivotal role in glycoscience. Recent substantial developments have poised the field to address emerging challenges related sustainability, cost efficiency, and robust applicability complex substrate settings. The transition from stoichiometric activation metal-catalyzed methods promises enhanced chemoselectivity greater precision controlling glycosidic bond breakage formation, key overcoming existing obstacles. Here, we report nitrene-mediated glycosylation strategy using regular aryl sulfide glycosyl donors easily accessible 3-methyl dioxazolone as an activator under catalysis of iron or ruthenium. iron-catalyzed system demonstrates exceptional catalytic reactivity, requiring little 0.1 mole % catalyst at room temperature, works well for peptide substrates. ruthenium-catalyzed can accommodate acid-sensitive functional groups challenging low-reactivity acceptors. Mechanistic investigations unveiled unusual multistep pathways involving sulfur imidation via nitrene transfer sulfur-to-oxygen rearrangement N-acyl sulfilimines donors.

Language: Английский

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Ligand‐Promoted Iron‐Catalyzed Nitrene Transfer for the Synthesis of Hydrazines and Triazanes through N‐Amidation of Arylamines

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

Published: Nov. 24, 2023

Abstract Herein, we report that bulky alkylphosphines such as P t Bu 3 can switch the roles from actor to spectator ligands promote FeCl 2 ‐catalyzed N ‐amidation reaction of arylamines with dioxazolones, giving hydrazides in high efficiency and chemoselectivity. Mechanistic studies indicated phosphine could facilitate decarboxylation dioxazolones on Fe center, hydrogen bonding interactions between nitrenoid intermediates might play a role modulating delicate interplay ligand, arylamine, acyl nitrene N, favoring N−N coupling over N−P coupling. The new ligand‐promoted protocols offer convenient way access various challenging triazane compounds via double or sequential primary arylamines.

Language: Английский

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Copper-Catalyzed Chemoselective Coupling of N-Dithiophthalimides and Alkyl Halides: Synthesis of Unsymmetrical Disulfides and Sulfides

Organic Letters, Journal Year: 2024, Volume and Issue: 26(17), P. 3634 - 3639

Published: April 25, 2024

In this paper, we report an unprecedented copper-catalyzed disulfides or sulfides coupling reaction involving unactivated alkyl halides and N-dithiophthalimides. This can be conducted under mild conditions using low-cost metal catalysts exhibits high chemical selectivity functional group compatibility, enabling the efficient assembly of various disulfides.

Language: Английский

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Heterogeneous photocatalytic synthesis of sulfenamides with carbon doped potassium poly(heptazine imide) through effective electron delocalization

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(15), P. 8785 - 8793

Published: Jan. 1, 2024

A ground-breaking light-driven strategy to synthesize sulfenamides using K-PHI-C doping is proposed. C-doping can extend optical absorption range near-infrared and create delocalized electronic density enhance the single electron transfer step.

Language: Английский

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Regio- and Enantioselective Catalytic δ-C–H Amidation of Dioxazolones Enabled by Open-Shell Copper-Nitrenoid Transfer

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(29), P. 16238 - 16248

Published: July 18, 2023

Controlling regio- and enantioselectivity in C-H functionalization reactions is of paramount importance due to their versatile synthetic utilities. Herein, we describe a new approach for the asymmetric δ-C(sp3)-H amidation catalysis dioxazolones using Cu(I) precursor with chiral bisoxazoline ligand access six-membered lactams high excellent (up >19:1 rr >99:1 er). Combined experimental computational mechanistic studies unveiled that open-shell character postulated Cu-nitrenoids enables regioselective hydrogen atom abstraction subsequent enantio-determining radical rebound resulting carbon intermediates. The utility this cyclization was demonstrated diastereoselective introduction additional functional groups into δ-lactam skeleton as well rapid biorelevant azacyclic compounds.

Language: Английский

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Selective S-Arylation of Sulfenamides with Arynes: Access to Sulfilimines

Organic Letters, Journal Year: 2023, Volume and Issue: 25(39), P. 7192 - 7197

Published: Sept. 21, 2023

Sulfilimines, the aza analogues of sulfoxides, are increasing interest in medicinal and agrochemical research programs. However, development efficient routes for their synthesis has remained relatively unexplored. In this study, we report a transition metal-free, selective S-arylation reaction between sulfenamides arynes, enabling facile preparation structurally diverse sulfilimines under mild redox-neutral conditions good yields. The application value our method was further demonstrated by scale-up synthesis, downstream derivatization, robustness screen.

Language: Английский

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Design of a Bilateral Disulfurating Reagent for Unsymmetrical Polysulfidation

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(25)

Published: April 22, 2023

In this study, we designed a bilateral disulfurating reagent via S-S motif "snip and stitch" processes, allowing diverse functional groups to be bridged bonds. The is readily synthesized in high yield using one-step reaction from easily available starting materials air-stable. With reagent, electrophiles including inactivated alkyl Cl/Br/I/OMs benzyl chloride were sequentially installed on either side of the motif. Natural products, agrochemicals, pharmaceuticals can successively cross-linked with Notably, used cyclic disulfide synthesis. At last, some desired products work showed good antibacterial activities, which could employed as novel candidates control plant pathogenic bacteria.

Language: Английский

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Synthesis of N‐Acylsulfenamides from (Hetero)Aryl Iodides and Boronic Acids by One‐Pot Sulfur‐Arylation and Dealkylation

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(3)

Published: Nov. 28, 2023

Abstract A general one‐pot approach to diverse N ‐acylsulfenamides from a common S ‐phenethylsulfenamide starting material is reported. This was demonstrated by C−S bond formation utilizing commercially abundant (hetero)aryl iodides and boronic acids provide sulfilimine intermediates that undergo thermal elimination of styrene. In contrast, all prior approaches rely on thiol inputs introduce sulfenamide ‐substituents. broad scope reaction including for approved drugs drug precursors with dense display functionality. Several different types sulfur functionalization were performed derived complex precursor the blockbuster anticoagulant apixaban, highlighting utility this introduction high oxidation state groups in bioactive compounds. Mechanistic studies established key styrene step proceeds concerted does not require reagents or catalysts, therefore, should be applicable synthesis electrophiles conditions formation.

Language: Английский

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An iron-catalyzed nitrene transfer reaction of nitrosobenzenes with N-acyloxyamides for accessing N-acyl azoxy molecules

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(9), P. 2561 - 2565

Published: Jan. 1, 2024

A nitrene transfer reaction of nitrosobenzenes with N -acyloxyamides using FeCl 2 ·4H O as a cheap and commercially available catalyst was developed for facile synthesis -acyl azoxy compounds high functional-group compatibility.

Language: Английский

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