Pro‐aromatic Dihydroquinazolinones – From Multigram Synthesis to Reagents for Gram‐scale Metallaphotoredox Reactions

Chemistry - An Asian Journal, Год журнала: 2023, Номер 19(3)

Опубликована: Дек. 16, 2023

Abstract Dihydroquinazolinone (DHQZ) has recently been harnessed as a ketone‐derived pro‐aromatic reagent extensively employed in (metalla)photoredox reactions versatile group transfer agents. In this work, we outline column chromatography‐free protocol for the multigram‐scale synthesis of DHQZs well its use gram‐scale nickel/photoredox dual‐catalyzed cross‐coupling single‐batch, photoflow, and simultaneous multiple smaller batches. While single‐batch approach leveraged moderate yields, simple plug‐flow photoreactor also exhibited amenable productivity (up to 45 % yield) despite heterogeneous base. Meanwhile, performing metallaphotoredox‐catalyzed reaction batches an improvised facilitated high yields up 59 good reproducibility, implying convenient alternative absence photoflow setups.

Язык: Английский

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Direct excitation strategy for deacylative couplings of ketones

Angewandte Chemie, Год журнала: 2024, Номер 136(42)

Опубликована: Июль 24, 2024

Abstract The homolysis of chemical bonds represents one the most fundamental reactivities excited molecules. Historically, it has been exploited to generate radicals under ultraviolet (UV) light irradiation. However, unlike contemporary radical‐generating mechanisms, direct excitation homolyze and produce aliphatic carbon‐centered visible remains rare, especially in metallaphotoredox cross couplings. Herein, we present our design dihydropyrimidoquinolinone (DHPQ) reagents derived from ketones, which can undergo formal deacylation homolytic C−C bond cleavage release alkyl without external photocatalysts. Spectroscopic computational analysis reveal unique optical structural features DHPQs, rationalizing their faster kinetics radical generation than a structurally similar but visible‐light transparent precursor. Such capability allows DHPQ facilitate wide range Ni‐metallaphotoredox couplings with aryl, alkynyl acyl halides. Other catalytic non‐catalyzed alkylative transformations DHPQs are also feasible various acceptors. We believe this work would be broad interest, aiding synthetic planning simplified operation expanding reach photocatalyst‐free approaches cutting‐edge research.

Язык: Английский

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Ketone Skeletal Modification via a Metallaphotoredox-Catalyzed Deacylation and Acylation Strategy

Organic Letters, Год журнала: 2024, Номер 26(44), С. 9503 - 9507

Опубликована: Окт. 28, 2024

Herein, we describe a dual catalytic strategy that employs dihydroquinazolinones, derived from ketone analogs, as versatile intermediates for acylation via α C–C cleavage with 2-pyridyl esters, facilitating the efficient synthesis of variety ketones. The reaction accommodates wide range ketones and carboxylic acids, showing tolerance to various functional groups. versatility this synthetic technique is further highlighted through its application in late-stage modification pharmaceuticals biologically active natural products.

Язык: Английский

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Synthesis of succinyldiamides containing all-quaternary carbon center by photo-induced amidation/smiles rearrangement of alkenes

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Дек. 23, 2024

A novel, mild, and environmentally friendly method was developed for the synthesis of quaternary-carbon-containing succinyldiamides. This found to be compatible with many substrates.

Язык: Английский

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Electrochemical C H alkylation of N-heterocycles via aromatization-driven C C fragmentation of unstrained ketones

Tetrahedron Letters, Год журнала: 2024, Номер 155, С. 155440 - 155440

Опубликована: Дек. 27, 2024

Язык: Английский

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