Stereoselective Synthesis of (Z)-Acrylic Nitriles from the Ruthenium-Catalyzed Coupling Reaction of Nitriles with Unsaturated Carbonyl Compounds via C–C Bond Cleavage DOI

Aldiyar Shakenov,

Krishna Prasad Gnyawali,

Chae S. Yi

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 90(5), P. 1733 - 1739

Published: Jan. 23, 2025

Acrylic nitriles are a versatile class of synthetic precursors for variety pharmaceutically active compounds, as well nitrile polymers. We devised stereoselective synthesis (Z)-acrylic from the Ru-catalyzed coupling reaction with unsaturated carbonyl compounds via C-C bond cleavage. Both carbon KIE and Hammett correlation data indicated that cleavage is rate-determining step reaction. Several bioactive were synthesized by using catalytic method.

Language: 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

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(8)

Published: Jan. 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

Language: Английский

Citations

24
Aromatization-driven deconstructive functionalization of spiro dihydroquinazolinones via dual photoredox/nickel catalysis DOI Creative Commons

Hong-Jie Miao,

Jinhua Zhang, Wenke Li

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(23), P. 8993 - 8999

Published: Jan. 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.

Language: Английский

Citations

20
Molecular Editing of Ketones through N-Heterocyclic Carbene and Photo Dual Catalysis DOI
Qing‐Zhu Li,

Mei-Hao He,

Rong Zeng

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(32), P. 22829 - 22839

Published: Aug. 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

Language: Английский

Citations

19
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

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(8)

Published: Dec. 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.

Language: Английский

Citations

47
Photocatalytic Deuterium Atom Transfer Deuteration of Electron‐Deficient Alkenes with High Functional Group Tolerance DOI
Akihiko Suzuki,

Yuji Kamei,

Masaaki Yamashita

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(3)

Published: Nov. 17, 2022

Abstract Due to its mild reaction conditions and unique chemoselectivity, hydrogen atom transfer (HAT) hydrogenation represents an indispensable method for the synthesis of complex molecules. Its analog using deuterium, deuterium (DAT) deuteration, is expected enable access deuterium‐labeled compounds. However, DAT deuteration has been scarcely studied synthetic purposes, a that possesses favorable characteristics HAT hydrogenations remained elusive. Herein, we report protocol photocatalytic electron‐deficient alkenes. In contrast previous this tolerates variety synthetically useful functional groups including haloarenes. The late‐stage also allows deuterated amino acids as well donepezil‐ d 2 . Thus, work demonstrates potential chemistry become alternative choice preparing deuterium‐containing

Language: Английский

Citations

41
Recent Advances in Deuteration Reactions† DOI
Hao Li, Shabbir Muhammad, Wu Li

et al.

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 42(10), P. 1145 - 1156

Published: Dec. 26, 2023

Comprehensive Summary The deuteration of organic compounds has attracted more attentions in recent years for the potential applications new drug discovery and synthetic chemistry. For this purpose, many efficient deuterium labeling methodologies have been developed, including hydrogen isotope exchange (HIE), reductive deuteration, dehalogenative that allow synthesis selectively deuterated compounds. In last few years, great breakthroughs selective achieved interest molecules is rising. review, we summarized developments since 2021. Several types key processes incorporation reactions, H/D exchange, are introduced discussed. Key Scientists 2000s, Derdau Atzrodt's group made contributions to directing assisted noble‐metal catalyzed arenes labeled During same period, Sajiki co‐workers completed a series reactions by heterogeneous platinum‐group metal catalysts. Since 2015, Gregory Pieters developed ruthenium catalysts exchange. 2016, Chirik's presence homogeneous iron complex. David MacMillan coworkers photocatalyzed HIE α‐amino C(sp 3 )–H bonds. From 2020, nanoelectrodes were designed deuterations unactivated unsaturated bonds Zhang's group. Recently, Beller's several strategies isotopic using earth‐abundant Our review latest important

Language: Английский

Citations

34
Visible-Light-Photocatalyzed Dicarbofunctionalization of Conjugated Alkenes with Ketone-Based Dihydroquinazolinones DOI
Pinku Prasad Mondal, Subham Das,

Sreelakshmi Venugopalan

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(9), P. 1441 - 1446

Published: Feb. 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.

Language: Английский

Citations

28
Deacylative arylation and alkynylation of unstrained ketones DOI Creative Commons
B. L. Zhang,

Hui Bai,

Bei‐Bei Zhan

et al.

Science Advances, Journal Year: 2024, Volume and Issue: 10(17)

Published: April 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

Language: Английский

Citations

11
Homologation of Ketones: Direct Transformation of Alkyl Ketones to Aryl Ketones via Photoredox Catalyzed Deacylation-Aroylation Sequence DOI
Tian Wang, Zengyu Zhang, Fan Gao

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(32), P. 6915 - 6920

Published: Aug. 8, 2024

Ketones, as essential functional group skeletons, have garnered significant interest due to their diverse transformations. Herein, we describe a versatile photoredox catalyzed deacylation-aroylation strategy that enables the direct transformation of alkyl ketones aryl ketones. This process involves deacylation dihydroquinazolinones derived from generate radicals, followed by subsequent NHC-catalyzed or NHC-mediated radical aroylation.

Language: Английский

Citations

10
Deacylative Thiolation by Redox‐Neutral Aromatization‐Driven C−C Fragmentation of Ketones DOI
Xukai Zhou,

Daniel Pyle,

Zining Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(15)

Published: Feb. 17, 2023

Herein we report the development of deacylative thiolation diverse methyl ketones. The reaction is redox-neutral, and heavy-metal-free, which provides a new way to introduce thioether groups site-specifically unactivated aliphatic positions. It also features excellent functional group tolerance broad substrate scope, thus allowing late-stage derivatization. process benefits from efficient condensation between activation reagent ketone substrates, triggers aromatization-driven C-C fragmentation rapid radical coupling with thiosulfonates. Experimental computational mechanistic studies suggest involvement chain pathway.

Language: Английский

Citations

23