2,2’‐Biquinoline‐Based Recyclable Electroauxiliaries for the Generation of Alkyl Radicals via C−C Bond Cleavage DOI Creative Commons
Shahilan Ratnam,

Shreya Unone,

Daniel Janßen-Müller

и другие.

Chemistry - A European Journal, Год журнала: 2023, Номер 29(50)

Опубликована: Июнь 2, 2023

Alkyl radical precursors are essential for a wide variety of photocatalytic and 3d-metal-catalyzed C-C bond forming reactions. Neutral organic heterocycles as electroauxiliaries such 4-alkyl Hantzsch esters have become reliable tools alkyl formation. Here we show that 2,2'-biquinoline-derived alkyl-substituted dihydroquinolines act competent with the ability to form primary, secondary tertiary radicals. Hydroalkylation benzalmalononitriles N-Boc protected diazenes has been achieved through copper catalysis under mild conditions 50 °C good very yields up 85 %. Furthermore, dihydroquinolines' reactivity towards denitrative alkylation nitroolefins β-nitrostyrene was discovered. Most importantly, released biquinoline can be recycled, which greatly improves overall atom-economy these in comparison previous N-heterocyclic electroauxiliaries.

Язык: Английский

Construction of C−S and C−Se Bonds from Unstrained Ketone Precursors under Photoredox Catalysis DOI Creative Commons
Hao Wu, Shuguang Chen,

Chunni Liu

и другие.

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

Процитировано

24

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

Hong-Jie Miao,

Jinhua Zhang, Wenke Li

и другие.

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

Процитировано

20

Copper‐Catalyzed C(sp3)‐Amination of Ketone‐Derived Dihydroquinazolinones by Aromatization‐Driven C−C Bond Scission DOI Creative Commons
Xin‐Yang Lv, Roman Abrams, Rubén Martı́n

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(8)

Опубликована: Дек. 28, 2022

Herein, we describe the development of a copper-catalyzed C(sp3 )-amination proaromatic dihydroquinazolinones derived from ketones. The reaction is enabled by intermediacy open-shell species arising homolytic C-C bond-cleavage driven aromatization. protocol characterized its operational simplicity and generality, including chemical diversification advanced intermediates.

Язык: Английский

Процитировано

46

Visible-Light-Photocatalyzed Dicarbofunctionalization of Conjugated Alkenes with Ketone-Based Dihydroquinazolinones DOI
Pinku Prasad Mondal, Subham Das,

Sreelakshmi Venugopalan

и другие.

Organic Letters, Год журнала: 2023, Номер 25(9), С. 1441 - 1446

Опубликована: Фев. 23, 2023

A visible-light-photocatalyzed 1,2-arylalkylation of N-(arylsulfonyl)acrylamides with ketone-based dihydroquinazolinones is described. The formal C-C bond cleavage aliphatic ketones unified tandem radical alkylation/1,4-aryl migration/desulfonylation to forge two different types vicinal bonds and construct an all-carbon quaternary α-stereocenter, thus enhancing the carbogenic complexity tolerating diverse functionalities. Additional telescopic synthesis product diversification, this method features a dicarbofunctionalization conjugated nucleophilic alkyl precursor (dihydroquinazolinone) utilizing oxygen as green oxidant at ambient temperature.

Язык: Английский

Процитировано

28

Molecular Editing of Ketones through N-Heterocyclic Carbene and Photo Dual Catalysis DOI
Qing‐Zhu Li,

Mei-Hao He,

Rong Zeng

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(32), С. 22829 - 22839

Опубликована: Авг. 1, 2024

The molecular editing of ketones represents an appealing strategy due to its ability maximize the structural diversity ketone compounds in a straightforward manner. However, developing efficient methods for arbitrary modification ketonic molecules, particularly those integrated within complex skeletons, remains significant challenge. Herein, we present unique recasting that involves radical acylation

Язык: Английский

Процитировано

17

Deacylative arylation and alkynylation of unstrained ketones DOI Creative Commons
B. L. Zhang,

Hui Bai,

Bei‐Bei Zhan

и другие.

Science Advances, Год журнала: 2024, Номер 10(17)

Опубликована: Апрель 26, 2024

Ketones are ubiquitous in bioactive natural products, pharmaceuticals, chemical feedstocks, and synthetic intermediates. Hence, deacylative coupling reactions enable the versatile elaboration of a plethora chemicals to access complex drug candidates products. Here, we present arylation alkynylation strategies for synthesis wide range alkyl-tethered arenes alkynes from cyclic ketones methyl under dual nickel/photoredox catalysis. This reaction begins by generating pre-aromatic intermediate (PAI) through condensation ketone

Язык: Английский

Процитировано

11

Photocatalytic C–C bond thio(seleno)esterification of 1,2-diketone-derived pro-aromatic intermediates DOI Creative Commons
Amit Pal, Soumya Sarkar,

Aaron Shibu

и другие.

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

Процитировано

1

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

Amit Dhibar,

Shruti Moorthy

и другие.

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

Процитировано

1

Photocatalytic Alkylation/Arylative Cyclization of N-Acrylamides of N-Heteroarenes and Arylamines with Dihydroquinazolinones from Unactivated Ketones DOI
Sandip Bag, Shubham Ojha,

Sreelakshmi Venugopalan

и другие.

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

Процитировано

16

Organophotoredox-Catalyzed Oxidative C(sp2)–H Alkylation of N-Heteroarenes with Dihydroquinazolinones by C–C Cleavage DOI

Sariga Mangalamundackal Vijayan,

Anagha Veluthanath Nair, Shubham Ojha

и другие.

Synlett, Год журнала: 2023, Номер 34(11), С. 1241 - 1246

Опубликована: Фев. 8, 2023

Abstract We report a visible-light-mediated, organophotoredox-catalyzed, C(sp2)–H alkylation of N-heteroarenes with dihydroquinazolines, prepared from aliphatic ketones, under oxidative conditions. This protocol represents metal-free approach to the effective construction C–C bonds through Minisci-type reaction, formally activating native C–H bond N-heteroarene and an α-C–C readily available ketone. The mild nature this method accommodates wide variety tolerating range functional groups.

Язык: Английский

Процитировано

14