Photoinduced Aromatization-Driven Deconstructive Fluorosulfonylation of Spiro Dihydroquinazolinones DOI

Wenpeng Yang,

Hong-Jie Miao,

Gang Wang

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 30, 2024

A catalyst-free photoinduced deconstructive fluorosulfonylation cascade of spiro dihydroquinazolinones with DABSO and NFSI is reported. This protocol features mild reaction conditions, good yields excellent functional group tolerance, providing a practical approach to the quinazolin-4(1H)-one-functionalized aliphatic sulfonyl fluorides. In addition, ease gram-scale synthesis versatility SuFEx exchange highlight application potential this protocol.

Language: Английский

Deacylative Homolysis of Ketone C(sp3)–C(sp2) Bonds: Streamlining Natural Product Transformations DOI
Michal Šimek, Sujit Mahato,

Brady W. Dehnert

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 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.

Language: Английский

Citations

1
Metal-free, photoredox-catalyzed aromatization-driven deconstructive functionalization of spiro-dihydroquinazolinones with α-CF3 alkenes DOI
Jinhua Zhang,

Hong-Jie Miao,

Jiayi Li

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(62), P. 8095 - 8098

Published: Jan. 1, 2024

Metal-free, photoredox-catalyzed aromatization-driven deconstructive functionalization of spiro-dihydroquinazolinones with α-CF 3 alkenes is achieved high chemoselectivity. Mechanistic studies suggest a radical pathway for this cascade reaction.

Language: Английский

Citations

4
Direct excitation strategy for deacylative couplings of ketones DOI
Jianbin Li, Ding Zhang, Lida Tan

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: July 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.

Language: Английский

Citations

4
Photocatalytic C–C Bond Azidation and Cyanation of Acyclic Ketones via a Pro-aromatic Intermediate DOI
Sandip Bag,

Amit Dhibar,

Shruti Moorthy

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 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.

Language: Английский

Citations

0
Copper‐Catalyzed Aromatization‐Driven Ring‐Opening Amination and Oxygenation of Spiro Dihydroquinazolinones DOI Open Access
Wenke Li,

Hong-Jie Miao,

Jinhua Zhang

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(58)

Published: Aug. 8, 2024

Abstract Mild and inexpensive copper‐catalyzed aromatization‐driven ring‐opening amination oxygenation of spiro dihydroquinazolinones are presented, respectively. These protocols provide facile atom‐economical access to the aminated carbonyl‐containing quinazolin‐4(3 H )‐ones in good yields with functional group compatibility, which difficult obtain by conventional methods. Remarkably, a telescoped procedure involving condensation ring‐opening/functionalization for simple cycloalkanone was found be accessible. Mechanistic studies suggest radical pathway this transformation.

Language: Английский

Citations

2
Visible Light-Promoted Aromatization-Driven Deconstructive Fluorination of Spiro Carbocycles DOI

Wenpeng Yang,

Hong-Jie Miao,

Le Liu

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(35), P. 7442 - 7446

Published: Aug. 26, 2024

A visible light-promoted aromatization-driven deconstructive fluorination of spiro carbocycles is presented. series dihydroquinazolinones reacted efficiently with NFSI under light irradiation to afford the 2-(4-fluoroalkyl)quinazolin-4(3H)-ones in good yields excellent functional group tolerance. radical pathway involving C–C bond cleavage and F atom transfer proposed for reaction. In addition, ring-opening chlorination NCS was also applicable.

Language: Английский

Citations

2
Regioselective C-C bond cleavage/aminocarbonylation cascade under copper catalysis DOI

Qi-Chao Shan,

Zhao Yan,

Yong Wu

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 28, 2024

Language: Английский

Citations

1
Direct excitation strategy for deacylative couplings of ketones DOI
Jianbin Li,

Ding Zhang,

Lida Tan

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(42)

Published: July 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.

Language: Английский

Citations

0
Photoinduced Aromatization-Driven Deconstructive Fluorosulfonylation of Spiro Dihydroquinazolinones DOI

Wenpeng Yang,

Hong-Jie Miao,

Gang Wang

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 30, 2024

A catalyst-free photoinduced deconstructive fluorosulfonylation cascade of spiro dihydroquinazolinones with DABSO and NFSI is reported. This protocol features mild reaction conditions, good yields excellent functional group tolerance, providing a practical approach to the quinazolin-4(1H)-one-functionalized aliphatic sulfonyl fluorides. In addition, ease gram-scale synthesis versatility SuFEx exchange highlight application potential this protocol.

Language: Английский

Citations

0