Merging SOMO activation with transition metal catalysis: Deoxygenative functionalization of amides to β-aryl amines

Science Advances, Год журнала: 2025, Номер 11(3)

Опубликована: Янв. 17, 2025

Singly occupied molecular orbital (SOMO) activation of in situ generated enamines has achieved great success (asymmetric) α-functionalization carbonyl compounds. However, examples on the use this mode transformations other functional groups are rare, and combination SOMO with transition metal catalysis is still less explored. In area deoxygenative functionalization amides, intermediates such as iminium ions were often to result formation α-functionalized amines. contrast, direct deoxygenation amides β-functionalized amines highly appealing yet remains scarcely investigated. Here, a arylation aryl halides was developed via multicatalysis iridium/photoredox/nickel/iridium, affording β-aryl high efficiency. The key reaction enamine synergy Ni-catalyzed arylation, which conjunction two compatible Ir-catalyzed reduction processes.

Язык: Английский

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Deoxygenative Nucleophilic Phosphonation and Electrophilic Alkylation of Secondary Amides: A Facile Access to Quaternary α-Aminophosphonates

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(7), С. 4357 - 4362

Опубликована: Фев. 9, 2024

The widespread occurrence and synthetic accessibility of amides render them valuable precursors for the synthesis diverse nitrogen-containing compounds. Herein, we present a metal-free streamlined strategy quaternary α-aminophosphonates. This approach involves sequential deoxygenative nucleophilic phosphonation versatile electrophilic alkylation secondary in one-pot fashion. Notably, this method enables direct bis-functionalization with both nucleophiles electrophiles first time, simple derivatization leading to free α-aminophosphonates by hydrolysis. protocol has advantages operational simplicity, broad functional-group compatibility, environmental friendliness, scalability multigram quantities.

Язык: Английский

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New Synthetic Approaches for the Construction of Enantioenriched Molecules Bearing Quaternary Stereocenters

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(21), С. 4294 - 4322

Опубликована: Авг. 17, 2024

Abstract Optically active molecule architectures stand as an important class of organic compounds and occupy a key role in academic industrial communities. Particularly, the molecules bearing quaternary carbon are vital importance because its favorable conformation valuable three‐dimensional molecules, which frequently play broad spectrum functional materials, pharmaceutical relevant natural agrochemicals. Over past few decades, large number synthetic strategies for enantioselective construction with chiral centers have been focus research initiatives. In this review, state‐of‐the‐art toward synthesis enantioenriched stereocenters summarized, could be segmented into four categories: 1) Construction optically by addition to prochiral sp 2 carbon; 2) all‐carbon via substitution at non‐chiral tetra‐substituted 3) kinetic resolution; 4) desymmetrization reactions.

Язык: Английский

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Transition‐Metal‐Free Radical Relay Cascade Annulation of Amides: Access to Antitumor Active Benzo[b]azepine and Oxindole Derivatives

Chemistry - A European Journal, Год журнала: 2024, Номер 30(63)

Опубликована: Авг. 26, 2024

Abstract Efficient transition‐metal‐free synthesis of benzo[b]azepines and oxindoles is achieved via a radical relay cascade strategy employing halogen atom transfer (XAT) for aryl generation followed by intramolecular hydrogen (HAT). Optimization yielded moderate to substantial yields under visible light irradiation. Preliminary biological assessments revealed promising anti‐tumor activity select compounds. This study underscores the potential XAT‐mediated cascades in medicinal chemistry anticancer drug discovery.

Язык: Английский

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Acid/Base-Tuned Asymmetric Reductive Heck and Denitrogenative Heck Reactions of In Situ-Formed α,β-Unsaturated Hydrazone

ACS Catalysis, Год журнала: 2024, Номер 15(1), С. 72 - 80

Опубликована: Дек. 13, 2024

Despite significant progress in the catalytic asymmetric 1,4-additions between various Michael donors and acceptors, exploration of organohalide remains elusive. Herein, we report Pd(0)-catalyzed intramolecular vinyl/aryl iodides to α,β-unsaturated hydrazones, featuring situ-formed hydrazone acid/base-tuned reaction pathways. Due its strong coordination ability, is capable steering C–C bond formation follow 1,4-addition mechanism instead conventional alkene insertion, thus enabling generation vinylhydrazinyl–Pd2+ species via Zimmerman–Traxler chairlike transition state. Notably, this preferentially undergoes protonation under acidic conditions, furnishing a reductive Heck with aid native hydrazine reductant, while it susceptible β-HN elimination basic conditions achieve denitrogenative reaction. The protocol affords highly enantioselective access diverse heterocycles, groups poised for further chemical manipulations.

Язык: Английский

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Graphical Abstract: Angew. Chem. Int. Ed. 6/2024

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(6)

Опубликована: Янв. 31, 2024

am Main, Germany.

Язык: Английский

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