Mechanochemical Copper-Catalyzed Synthesis of NH-Sulfonimidamides by Oxidative Amination of Primary Sulfinamides

ACS Sustainable Chemistry & Engineering, Journal Year: 2024, Volume and Issue: 12(43), P. 15875 - 15880

Published: Oct. 15, 2024

A mechanochemical copper-catalyzed oxidative amination of primary sulfinamides has been developed, leading to NH-sulfonimidamides in moderate good yields under solvent-free conditions. Air serves as a terminal oxidant without the need for external additives. The obtained products could be readily converted into both acyclic and cyclic sulfonimidamide derivatives. This approach demonstrates considerable ecological benefits compared solvent-based methods.

Language: Английский

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Photocatalyzed Azidofunctionalization of Alkenes via Radical‐Polar Crossover

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

The azidofunctionalization of alkenes under mild conditions using commercially available starting materials and easily accessible reagents is reported based on a radical-polar crossover strategy. A broad range alkenes, including vinyl arenes, enamides, enol ethers, sulfides, dehydroamino esters, were regioselectively functionalized with an azide nucleophiles such as azoles, carboxylic acids, alcohols, phosphoric oximes, phenols. method led to more efficient synthesis 1,2-azidofunctionalized pharmaceutical intermediates when compared previous approaches, resulting in both reduction step count increase overall yield. scope limitations these transformations further investigated through standard unbiased selection 15 substrate combinations out 1,175,658 possible clustering technique.

Language: Английский

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Photocatalyzed Azidofunctionalization of Alkenes via Radical‐Polar Crossover

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

Abstract The azidofunctionalization of alkenes under mild conditions using commercially available starting materials and easily accessible reagents is reported based on a radical‐polar crossover strategy. A broad range alkenes, including vinyl arenes, enamides, enol ethers, sulfides, dehydroamino esters, were regioselectively functionalized with an azide nucleophiles such as azoles, carboxylic acids, alcohols, phosphoric oximes, phenols. method led to more efficient synthesis 1,2‐azidofunctionalized pharmaceutical intermediates when compared previous approaches, resulting in both reduction step count increase overall yield. scope limitations these transformations further investigated through standard unbiased selection 15 substrate combinations out 1,175,658 possible clustering technique.

Language: Английский

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Concerted or Stepwise? An Experimental and Computational Study to Reveal the Mechanistic Change as a Result of the Substituent Effects

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 6, 2025

This study investigates the Cope elimination reaction, focusing on mechanistic shift between concerted and stepwise pathways influenced by substituent effects. Experimental approaches, including kinetic isotope effects (KIEs) linear free energy relationships (LFERs), alongside density functional theory (DFT) computations, were employed to explore influence of substituents reaction kinetics pathways. Our findings reveal temperature- substituent-dependent partitioning syn-β E1cB mechanism, providing deeper insights into diversity reactions.

Language: Английский

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Stereodivergent Synthesis of Complex N-Sulfonimidoyl Lactams via the Castagnoli–Cushman Reaction

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 29, 2025

The reactivity between sulfonimidamide-derived imines and cyclic anhydrides has been investigated. Sulfonimidamide readily react with homophthalic anhydride under mild conditions in the presence of non-nucleophilic bases to yield complex lactam products high diastereoselectivity. Furthermore, it was discovered that sulfonimidamide absence a base distinct diastereomer Density functional theory calculations suggest existence an open transition state pathway novel eight-membered base.

Language: Английский

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Asymmetric S=N-embedded polyaromatic construction via enantioselective Pd-catalyzed C–H activation

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: March 28, 2025

Heteroatom-doped polyaromatic hydrocarbons show great potential for advancing photoelectric materials. SVI=N doping, characterized by soft-hard atom binding, donor-acceptor transmission, and chiroptical tuning, provides a powerful approach further optimizing the performance functionality of these However, introduction chiral sulfur(VI) has been formidable challenge due to intricate enantioselective discrimination embedded linkages with heteroatoms in systems. Herein, we establish an Pd-catalyzed desymmetrization diaryl sulfoximines sulfondiimines access SVI=N-doped heterocycles high yields enantioselectivities. The flexibility rigidity molecule distinct effect on enantioselectivity. split aromatic compounds exhibit C-H···π interactions involving additive TMCPA ligand S-aryl motif, producing (R)-configuration, while combined opposite (S)-configuration restricted bond rotation. photophysical study demonstrates carbazole-based heterocycle intense double absorption peaks favorable luminescence dissymmetry factor.

Language: Английский

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Mechanochemical syntheses of N-acyl sulfinamidines via iron-nitrenoids and their conversions to sulfur(VI) derivatives

Green Synthesis and Catalysis, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

Language: Английский

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A meta-learning approach for selectivity prediction in asymmetric catalysis

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: April 15, 2025

Abstract Transition metal-catalyzed asymmetric reactions are of high contemporary importance in organic synthesis. Recently, machine learning (ML) has shown promise accelerating the development newer catalytic protocols. However, need for large amount experimental data can present a bottleneck implementing ML models. Here, we propose meta-learning workflow that harness literature-derived to extract shared reaction features and requires only few examples predict outcome new reactions. Prototypical networks used as method enantioselectivity hydrogenation olefins. This model consistently provides significant performance improvement over other popular methods such random forests graph neural networks. The our meta-model is analyzed with varying sizes training demonstrate its utility even limited data. A good on an out-of-sample test set further indicates general applicability approach. We believe this work will provide leap forward identifying promising early phases when minimal available.

Language: Английский

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High-throughput experimentation and machine learning-promoted synthesis of α-phosphoryloxy ketones via Ru-catalyzed P(O)O-H insertion reactions of sulfoxonium ylides

Science China Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 10, 2024

Language: Английский

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Enantioselective Synthesis of Chiral Sulfonimidoyl Fluorides Facilitates Stereospecific SuFEx Click Chemistry

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

Published: Nov. 5, 2024

Abstract Sulfur‐centered electrophilic ‘warheads’ have emerged as key components for chemical proteomic probes through sulfur‐exchange chemistry (SuFEx) with protein nucleophiles. Among these functional groups, sulfonimidoyl fluorides (SIFs) stand out their modifiable sites, tunable electrophilicities, and chiral sulfur‐center, presenting exciting possibilities new covalent probes. However, the synthetic access to SIFs has been a challenge, limiting exploration applications. In this study, we describe convenient route obtain from readily available sulfenamides via series of one‐pot tandem reactions high enantiomeric excess (ees). The resulting were further converted into diverse array S(VI) derivatives under mild conditions or in buffer solutions. Most significantly, specificity ligation experiments underscored critical role sulfur‐center chirality design screening more‐selective therapeutics.

Language: Английский

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