Photocatalyzed Azidofunctionalization of Alkenes via Radical‐Polar Crossover

Angewandte Chemie, Год журнала: 2025, Номер unknown

Опубликована: Янв. 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.

Язык: Английский

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Recent Advances in Single-Electron Reduction-Induced Ring Opening of N-Acyl Cyclic Amines

Synthesis, Год журнала: 2025, Номер unknown

Опубликована: Янв. 16, 2025

Abstract Cyclic amines represent ubiquitous structural motifs in organic chemistry, prominently featured natural products and pharmaceuticals. The development of synthetic methodologies targeting cyclic has attracted considerable interest, given their significance medicinal chemistry. These transformations can be broadly categorized into two main types: (1) peripheral modification (2) skeletal remodeling. Recent advancements late-stage C–H functionalization have showcased the potential strategies. Conversely, remodeling, particularly through ring opening amines, emerged as a powerful approach to access structurally diverse amines. Ring initiated by C–N bond cleavage, predominantly relies on two-electron mechanisms. Strained readily undergo such transformations, while those with larger-membered ring, like pyrrolidines, present greater challenges. Oxidative von Braun-type approaches facilitated heterolytic offering broad applicability across various In contrast, reductive approaches, which enable homolytic provide unique radical-mediated transformations. This short review highlights recent progress single electron reduction induced ring-opening methodologies, focusing α-aminoketyl radical generation for selective amide cleavage. Advances aziridines, azetidines, other are discussed, along implications future prospects. 1 Introduction 2 Opening Aziridines 2.1 Hydrogenation Alkylation 2.2 Isomerization 2.3 Arylation 3 Azetidines 4 Pyrrolidines Other Amines 5 Conclusion Outlook

Язык: Английский

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Revealing the Relationship between Publication Bias and Chemical Reactivity with Contrastive Learning

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

Опубликована: Март 2, 2025

A synthetic method's substrate tolerance and generality are often showcased in a "substrate scope" table. However, selection exhibits frequently discussed publication bias: unsuccessful experiments or low-yielding results rarely reported. In this work, we explore more deeply the relationship between such bias chemical reactivity beyond simple analysis of yield distributions using novel neural network training strategy, scope contrastive learning. By treating reported substrates as positive samples nonreported negative samples, our learning strategy teaches model to group molecules within numerical embedding space, based on historical trends published tables. Training 20,798 aryl halides CAS Content CollectionTM, spanning thousands publications from 2010 2015, demonstrate that learned embeddings exhibit correlation with physical organic descriptors through both intuitive visualizations quantitative regression analyses. Additionally, these applicable various reaction modeling tasks like prediction regioselectivity prediction, underscoring potential use data pretraining task. This work not only presents chemistry-specific machine learn literature new way but also represents unique approach uncover reflected by publications.

Язык: Английский

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Asymmetric Synthesis of 10-Demethoxyvincorine Enabled by Dual Ni/Ti-Catalyzed Reductive Cyclization

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 10, 2025

Herein, we report the asymmetric synthesis of 10-demethoxyvincorine in 12 steps. The is highlighted by several key transformations: (1) a Pd-catalyzed Catellani-type reaction for preparation C2-alkylated tryptamine, (2) chiral phosphoric acid (CPA)-catalyzed bromocyclization to construct enantioenriched 3a-bromo-hexahydropyrroloindoline, (3) dual Ni/Ti-catalyzed reductive cyclization establish bridged ring system, and (4) SmI2-promoted forge strained E-ring.

Язык: Английский

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Green Light Promoted Iridium(III)/Copper(I)‐Catalyzed Addition of Alkynes to Aziridinoquinoxalines Through the Intermediacy of Azomethine Ylides

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(12)

Опубликована: Янв. 25, 2024

This manuscript describes the development of alkyne addition to aziridine moiety aziridinoquinoxalines using dual Ir(III)/Cu(I) catalytic system under green light-emitting diode (LED) photolysis (λ

Язык: Английский

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β‐Phenethylamine Synthesis: N‐Pyridinium Aziridines as Latent Dual Electrophiles

Angewandte Chemie, Год журнала: 2024, Номер 136(31)

Опубликована: Май 3, 2024

Abstract β ‐Phenethylamines are widely represented in biologically and pharmacologically active organic small molecules. Here, we introduce N ‐pyridinium aziridines as latent dual electrophiles for the synthesis of ‐phenethylamines. Bromide‐promoted ring opening generates ‐halopyridinium amines. Selective Ni‐catalyzed C−C cross‐coupling between organozinc nucleophiles benzylic C−Br electrophile affords a diverse family β‐ functionalized phenethylaminopyridinium salts, coupling is stereoconvergent presence chiral ligands. Subsequent reductive N−N bond activation within salts furnishes products formal olefin carboamination. Other cleavage reactions demonstrated to provide access free primary amines, alkylated heterocycles, derived from N‐ centered radical chemistry. The developed reaction sequence can be implemented context complex molecules natural product derivatives. Together, described results general modular phenethylamines significantly expand utility linchpins chemical synthesis.

Язык: Английский

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Effects of Metal–Metal Bonding in Photosensitizers: Red-Shifted Absorption and Oscillator Strength Enhancement

Inorganic Chemistry Frontiers, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Metal–metal bonds facilitate a red-shift in the maximum absorption wavelength and an enhancement of oscillator strength photosensitizers.

Язык: Английский

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Aziridines as Versatile C(sp3) Precursors in Transition-Metal Catalyzed Cross-Coupling Strategies

Synthesis, Год журнала: 2024, Номер unknown

Опубликована: Окт. 6, 2024

Abstract Aziridines, which serve as valuable scaffolds in numerous pharmaceuticals and bioactive molecules, have emerged highly efficient C(sp3) precursors the realm of organic chemistry. Particularly, employing aziridines versatile electrophiles transition-metal-catalyzed cross-coupling has enabled precise control over regiochemistry formation new C(sp3)–C, –Si, –B bonds. This review explores recent innovative aziridine approaches using Ni or Pd catalysis, highlighting initial findings mechanistic delineating distinct catalytic pathways. 1 Introduction 2 Aziridines Used Precursors with Organometallic Reagents 2.1 Ni-Catalyzed Aziridine Cross-Coupling 2.2 Pd-Catalyzed 3 Net-Reductive Approaches via Cross-Electrophile Coupling 3.1 Using Chemical Reductants 3.2 Electrochemical Reductions 4 Metallaphotoredox Catalysis 4.1 Metallaphotoredox-Catalyzed 4.2 Redox-Neutral 5 Miscellaneous 6 Conclusion Future Outlook

Язык: Английский

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Synthesis of Phenethylamine‐Azulene Conjugates Enabled by Regioselective Ring Opening of Aziridines

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 366(4), С. 1007 - 1012

Опубликована: Ноя. 21, 2023

Abstract The BF 3 ⋅OEt 2 ‐catalyzed reaction of azulene with N ‐protected aziridines represents a general, efficient (up to 91% yield) and regioselective approach phenethylamine‐azulene conjugates. Stereochemical studies DFT calculations lend support concerted S 2‐type mechanism governing the ring‐opening aziridine.

Язык: Английский

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Magnesium catalyzed asymmetric ring-opening reactions of high-strained three membered cyclic systems

Chinese Science Bulletin (Chinese Version), Год журнала: 2023, Номер unknown

Опубликована: Дек. 1, 2023

Язык: Английский

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