Photoredox‐Catalyzed α−C−H Monoalkylation of Symmetric Polyols in the Presence of CO2 DOI

Gaétan Archer,

Ricardo Meyrelles,

Isabel Eder

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(6)

Published: Dec. 13, 2023

Abstract Achieving the selective modification of symmetric poly‐hydroxylated compounds presents a significant challenge due to presence identical active sites. Herein, we address this through design ternary catalytic system that includes photoredox catalyst, hydrogen atom transfer promotor and carbonation catalyst. This enables reversible acyclic polyols under CO 2 atmosphere, which modulates reactivity its distinct C−H bonds toward transfers. An exquisite selectivity for monoalkylation is achieved in variety unprotected light polyols, yielding valuable building blocks short reaction times. Mechanistic computational studies demonstrate formation an intramolecular bond between transient carbonate free alcohol pivotal kinetic thermodynamic activation specific alcohol.

Language: Английский

Advances in photoinduced radical–polar crossover cyclization (RPCC) of bifunctional alkenes DOI
Meng Liu,

Xinke Ouyang,

C. Nguyen Xuan

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 11(3), P. 895 - 915

Published: Dec. 20, 2023

Photoinduced radical–polar crossover cyclization (RPCC) of bifunctional alkenes is high synthetic utility to produce cyclic products with precise alkene design. This review summarizes the recent representative advances in field RPC.

Language: Английский

Citations

25
Shedding light on thermally-activated delayed fluorescence DOI Creative Commons
Francesco Di Maiolo, D. K. Andrea Phan Huu, Davide Giavazzi

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(15), P. 5434 - 5450

Published: Jan. 1, 2024

To exploit the applicative potential of TADF, several intertwined interactions must be understood, fully accounting for local environment.

Language: Английский

Citations

14
Photoinduced radical-polar crossover cyclization reactions DOI
Zhiming Zhu, Yongxin Zhang, Ziyang Li

et al.

Chem Catalysis, Journal Year: 2024, Volume and Issue: 4(5), P. 100945 - 100945

Published: March 5, 2024

Language: Английский

Citations

14
Exploration of Light Mediated Strategies in Four Membered Heterocycle Synthesis DOI
Suman Majee, Km. Anjali, Bimal Krishna Banik

et al.

Tetrahedron, Journal Year: 2025, Volume and Issue: unknown, P. 134493 - 134493

Published: Jan. 1, 2025

Language: Английский

Citations

1
Photoinduced arylative formal 4-endo-dig cyclization of propargyl alcohols/amines to access strained heterocycles DOI
Pammi Venka Reddy, Attunuri Nagireddy, Jagadeesh Babu Nanubolu

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(5), P. 2705 - 2711

Published: Jan. 1, 2024

A novel synthetic strategy to access strained heterocycles is revealed through photocatalysed annulative formal 4- endo-dig cyclization of propargyl alcohols/amines with benzoquinones under catalyst/reagent-free conditions using non-hazardous solvent.

Language: Английский

Citations

6
Enhancing Electron Donor–Acceptor Complex Photoactivation with a Stable Perylene Diimide Metal–Organic Framework DOI Creative Commons
Xia Wu, Ming Cui, Kun Wu

et al.

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

Published: Jan. 27, 2025

Electron donor–acceptor complexes are commonly employed to facilitate photoinduced radical-mediated organic reactions. However, achieving these photochemical processes with catalytic amounts of donors or acceptors can be challenging, especially when aiming reduce catalyst loadings. Herein, we have unveiled a framework-based heterogenization approach that significantly enhances the photoredox activity perylene diimide species in radical addition reactions alkyl silicates by promoting faster and more efficient electron complex formation. Besides offering broad substrate scope alkene hydroalkylation, newly developed heterogeneous photocatalysis substantially improves turnover numbers comparison previous homogeneous photocatalytic systems demonstrates outstanding recyclability. These research findings pave way for advancement various practical transformations using framework-supported organocatalysts.

Language: Английский

Citations

0
Biocatalytic enantioselective formation and ring-opening of oxetanes DOI Creative Commons
Xia Hua, Yuanfei Wang, Xiao Jin

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 30, 2025

Although biocatalysis offers complementary or alternative approaches to traditional synthetic methods, the limited range of available enzymatic reactions currently poses challenges in synthesizing a diverse array desired compounds. Consequently, there is significant demand for developing novel biocatalytic processes enable that were previously unattainable. Herein, we report discovery and subsequent protein engineering unique halohydrin dehalogenase develop platform enantioselective formation ring-opening oxetanes. This platform, exhibiting high efficiency, excellent enantioselectivity, broad scopes, facilitates preparative-scale synthesis chiral oxetanes variety γ-substituted alcohols. Additionally, both oxetane are proven scalable large-scale transformations at substrate concentrations, can be integrated efficiently one-pot, one-catalyst cascade system. work expands toolbox non-natural will promote further exploration catalytic repertoire dehalogenases pharmaceutical chemistry. Oxetane four-membered, oxygen-containing heterocyclic compound importance medicinal chemistry drug development. Here, authors dehalogenase,

Language: Английский

Citations

0
Harnessing Oxetane and Azetidine Sulfonyl Fluorides for Opportunities in Drug Discovery DOI Creative Commons
Oliver L. Symes, Hikaru Ishikura,

Callum S. Begg

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 12, 2024

Four-membered heterocycles such as oxetanes and azetidines represent attractive emergent design options in medicinal chemistry due to their small polar nature potential significantly impact the physiochemical properties of drug molecules. The challenging preparation these derivatives, especially a divergent manner, has severely limited combination with other medicinally biologically important groups. Consequently, there is substantial demand for mild effective synthetic strategies access new oxetane azetidine derivatives molecular scaffolds. Here, we report development use sulfonyl fluorides (OSFs) (ASFs), which behave precursors carbocations an unusual defluorosulfonylation reaction pathway (deFS). small-ring are activated under thermal conditions (60 °C), generated reactive intermediates couple broad range nucleophiles. Oxetane heterocyclic, -sulfoximine, -phosphonate prepared, several do not have comparable carbonyl analogs, providing chemical motifs elements discovery. Alternatively, SuFEx anionic accesses oxetane-sulfur(VI) derivatives. We demonstrate utility novel OSF ASF reagents through synthesis 11 showcasing subsequent diversification facile inclusion into programs. Moreover, propose application linker incorporation pendant groups suitable common conjugation reactions. Productive deFS reactions E3 ligase recruiters pomalidomide related provide degrader PROTAC linkers.

Language: Английский

Citations

3
Diastereoselective Synthesis of Pyrroloquinolines via N–H Functionalization of Indoles with Vinyl Sulfonium Salts DOI

Ruiying Ma,

Zijie Zhou,

Peng Yang

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 89(1), P. 452 - 462

Published: Dec. 12, 2023

A [2 + 4]/[1 2] annulation approach was successfully established to construct pyrroloquinoline-fused cyclopropane in a highly diastereoselective fashion (>20:1 dr). The tetracyclic 1,7-fused indoles were efficiently obtained from readily available starting materials under mild conditions. This methodology displays impressive substrate generality with two reaction components. products resulting this doubly annulative strategy are useful synthetic intermediates.

Language: Английский

Citations

4
Synthesis of Alcohols: Streamlined C1 to Cn Hydroxyalkylation through Photoredox Catalysis DOI Creative Commons

F Pasca,

Yuri Gelato,

Michael Andresini

et al.

Published: March 6, 2024

Naturally occurring and readily available α-hydroxy carboxylic acids (AHAs) are utilized as platforms for visible light-mediated oxidative CO2-extrusion furnishing radicals proved to be versatile C1 Cn hydroxyalkylating agents. The decarboxylative direct Giese reaction (DDGR) is operationally simple, not requiring activator or sacrificial oxidants, enables the synthesis of a diverse range hydroxylated products, introducing connectivity typically precluded from conventional polar domains. Notably, methodology has been extended widely used glycolic acid resulting in highly efficient unprecedented hydroxyhomologation tactic. use flow technology further facilitates scalability adds green credentials this synthetic methodology.

Language: Английский

Citations

1