Construction of C−S and C−Se Bonds from Unstrained Ketone Precursors under Photoredox Catalysis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(8)

Опубликована: Янв. 8, 2024

A mild photoredox catalyzed construction of sulfides, disulfides, selenides, sulfoxides and sulfones from unstrained ketone precursors is introduced. Combination this deacylative process with S

Язык: Английский

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Aromatization-driven deconstructive functionalization of spiro dihydroquinazolinones via dual photoredox/nickel catalysis

Chemical Science, Год журнала: 2024, Номер 15(23), С. 8993 - 8999

Опубликована: Янв. 1, 2024

The aromatization-driven deconstructive coupling of spiro carbocycles with organic halides via dual photoredox/nickel catalysis is developed. An in-depth mechanism study revealed that this reaction proceeded a radical-metal crossover pathway.

Язык: Английский

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Decatungstate‐Photocatalyzed Diastereoselective Dearomative Hydroalkylation of Indoles

European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(22)

Опубликована: Апрель 16, 2024

Abstract In this study, we present an efficient and straightforward dearomative hydroalkylation of indoles. By utilizing alkanes or ethers as alkyl radical sources employing TBADT a cost‐effective photocatalyst for direct hydrogen atom transfers (HAT), achieved successful conversion these heterocyclic derivatives into 2‐alkylindolines with good to excellent yields high diastereoselectivity under mild reaction conditions.

Язык: Английский

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Deacylative Homolysis of Ketone C(sp³)–C(sp²) Bonds: Streamlining Natural Product Transformations

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

Опубликована: Янв. 7, 2025

The homolytic cleavage of C–C bonds adjacent to specific functional groups has lately emerged as a versatile approach for molecular diversification. Despite the ubiquity and synthetic utility ketones, radical fragmentation their α-C–C proven be formidable challenge. Here, we present broadly applicable deacylative strategy designed homolytically cleave aliphatic ketones various complexities, including transformations cycloalkanones into carboxylic acids tethered C-centered free radicals that can engaged in diverse radical-based processes. method involves ketone activation through treatment with hydrogen peroxide, yielding gem-dihydroperoxides. Subsequent single-electron-transfer reduction mediated by low-valent metal complex generates alkyl captured selectively radicophile choice, catalytic cross-coupling. logic our functionalization is exemplified total synthesis 14 natural products, one analogue, two drugs starting from readily available showcasing its transformative power settings. This obviates need reagents allows controlled conversion reconstructed making process highly across spectrum domains.

Язык: Английский

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Photocatalytic Alkylation/Arylative Cyclization of N-Acrylamides of N-Heteroarenes and Arylamines with Dihydroquinazolinones from Unactivated Ketones

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(16), С. 12121 - 12130

Опубликована: Июль 29, 2023

We describe a visible-light photoredox-catalyzed alkylation/arylative cyclization of N-acrylamides─from 2-arylindoles, 2-arylbenzimidazoles, or N-substituted anilines─with ketone-derived dihydroquinazolinones, accessing indolo- and benzimidazolo[2,1-a]isoquinolines 2-oxindoles. The consecutive incorporation alkyl- aryl-carbogenic motifs across C=C bond via formal cleavage ketone α-C-C arene C-H bonds leads to the formation five- six-membered rings, with an all-carbon quaternary stereocenter. This dicarbofunctionalization elaborates aromatization-driven radical C-C functionalization unactivated aliphatic ketones construct diverse cyclic structures functionality tolerance.

Язык: Английский

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Direct excitation strategy for deacylative couplings of ketones

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

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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Photocatalytic C–C Bond Azidation and Cyanation of Acyclic Ketones via a Pro-aromatic Intermediate

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Янв. 10, 2025

Herein, we report a formal C–C bond azidation and cyanation of unactivated aliphatic ketones using commercially available tosyl azide cyanide, respectively. A visible-light-mediated organophotocatalyst enables radical ketone-derived pro-aromatic dihydroquinazolinones (under mostly redox-neutral conditions) as supported by preliminary mechanistic studies. These metal-free scalable protocols can be used to synthesize tertiary, secondary, primary alkyl azides nitriles with good functional group tolerance postsynthetic diversification the group, including bioconjugation.

Язык: Английский

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Photocatalytic C–C bond thio(seleno)esterification of 1,2-diketone-derived pro-aromatic intermediates

Chemical Communications, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

We report an organophotocatalyst-enabled oxidant-free C–S/C–Se bond coupling of (un)symmetrical 1,2-diketones via pro-aromatic dihydroquinazolinones/benzothiazolines, employing readily accessible disulfides/diselenides.

Язык: Английский

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Organo-Photoredox Catalyzed gem-Difluoroallylation of Ketone-Derived Dihydroquinazolinones with α-Trifluoromethyl Alkenes via C(sp3)-C Bond and C(sp3)-F Bond Cleavage

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(27), С. 5561 - 5568

Опубликована: Янв. 1, 2024

An organo-photoredox catalyzed defluorinative alkylation of ketone-derived dihydroquinazolinones with α-trifluoromethyl alkenes is described, providing a facile access to diverse set gem -difluoroalkenes.

Язык: Английский

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2‐Silylated Dihydroquinazolinone as a Photocatalytic Energy Transfer Enabled Radical Hydrosilylation Reagent

Chemistry - A European Journal, Год журнала: 2023, Номер 29(45)

Опубликована: Июнь 3, 2023

The hydrosilylation of alkenes is one the most important methods for synthesis organosilicon compounds. In addition to platinum-catalyzed hydrosilylation, silyl radical reactions are notable as economic reactions. An efficient and widely applicable reaction was developed by using 2-silylated dihydroquinazolinone derivatives under photocatalytic conditions. Electron-deficient styrene underwent give products in good high yields. Mechanistic studies indicated that photocatalyst functioned not a photoredox catalyst but an energy transfer catalyst. DFT calculations clarified triplet excited state released through homolytic cleavage carbon-silicon bond, this followed hydrogen atom pathway, redox pathway.

Язык: Английский

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