A Ketone Synthesis via Cu(I)-Catalyzed Regioselective Coupling of 2-Pyridylthioesters with Grignard Reagents: In Quest of Straightforward Access to Pharmaceuticals DOI
Masahiko Seki,

Shaheen Kasim Mulani,

Runlin Yang

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 5, 2025

For commercial production of SGLT2 inhibitors, cryogenic conditions (-78 °C) were required at the key C-glycosidation step, which has restricted their supply to world market. To address challenge, reported herein is a new synthetic method based on ketone synthesis by means copper(I)-catalyzed coupling 2-pyridylthioesters with Grignard reagents. The facile transformation from ketones final APIs was realized under mild due use readily cleavable acetyl protecting groups.

Language: Английский

Recent Advances in Electron Donor‐Acceptor (EDA)‐Complex Reactions involving Quaternary Pyridinium Derivatives DOI

Barakha Saxena,

Roshan I. Patel,

Anuj Sharma

et al.

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(10), P. 1538 - 1564

Published: March 6, 2023

Abstract Quaternary pyridinium compounds are valuable intermediates in organic synthesis, which have gained immense popularity the synthetic community. The application of transition metal or photoredox catalysis transforming quaternary into various C−C and C−X bonds is well established. A majority these methods require high temperatures, expansive catalysts, delicate conditions for successful execution. On other hand, use metal‐free photocatalysis‐free strategies constructing using derivatives has been sought‐after. In this context, electron‐donor‐acceptor (EDA)‐complex reactions emerged as a state‐of‐the‐art methodology, do not any photocatalyst their EDA‐complex photochemistry takes advantage electron‐acceptor ability derivatives, can quickly generate radical precursor via deaminative process. These newly generated useful several transformations. We hereby, review, discuss an area major progress mediated involving with mechanism, substrate scope, limitations. magnified image

Language: Английский

Citations

43
Harnessing alcohols as sustainable reagents for late-stage functionalisation: synthesis of drugs and bio-inspired compounds DOI
Sourajit Bera, Lalit Mohan Kabadwal, Debasis Banerjee

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(9), P. 4607 - 4647

Published: Jan. 1, 2024

This review collectively discussed the utilisation of alcohols in various organic transformations and their application toward intermediates drugs, drug derivatives natural product-like molecules.

Language: Английский

Citations

16
Methyl gallate: Review of pharmacological activity DOI Creative Commons

Huaguo Liang,

Qingsong Huang,

Li Zou

et al.

Pharmacological Research, Journal Year: 2023, Volume and Issue: 194, P. 106849 - 106849

Published: July 8, 2023

Methyl gallate (MG) is a polyphenolic compound widely found in natural plants. MG has been shown to have variety of biological functions, including anti-tumor, anti-inflammatory, anti-oxidant, neuroprotective, hepatoprotective and anti-microbial activities, broad research development prospects. A total 88 articles related were searched using the PubMed, Science Direct, Google Scholar databases, systematically investigating pharmacological activity molecular mechanisms MG. There no restrictions on publication years, last search was conducted June 5, 2023. can exert effects through multiple pathways targets, such as PI3K/Akt, ERK1/2, Caspase, AMPK/NF-κB, Wnt/β-catenin, TLR4/NF-κB, MAPK, p53, NLRP3, ROS, EMT. According literature, potential be prospective adjuvant for anticancer therapy deserves further study.

Language: Английский

Citations

38
Oxidative rearrangement of 1,1-disubstituted alkenes to ketones DOI
Qiang Feng, Qian Wang, Jieping Zhu

et al.

Science, Journal Year: 2023, Volume and Issue: 379(6639), P. 1363 - 1368

Published: March 31, 2023

The Wacker process, which is widely used to convert monosubstituted alkenes into the corresponding methyl ketones, thought proceed through a PdII/Pd0 catalytic cycle involving β-hydride elimination step. This mechanistic scenario inapplicable synthesis of ketones from 1,1-disubstituted alkenes. Current approaches based on semi-pinacol rearrangement PdII intermediates are limited ring expansion highly strained methylene cyclobutane derivatives. Herein, we report solution this synthetic challenge by designing PdII/PdIV incorporating 1,2-alkyl/PdIV dyotropic as key reaction, compatible with broad range functional groups, applicable both linear olefins and cycloalkanes, including macrocycles. Regioselectivity favors migration more substituted carbon, strong directing effect β-carboxyl group was also observed.

Language: Английский

Citations

31
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

26
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

15
Alcohols as Alkyl Synthons Enabled by Photoredox-Catalyzed Deoxygenative Activation DOI

Tanumoy Mandal,

Samrat Mallick,

Malekul Islam

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(17), P. 13451 - 13496

Published: Aug. 26, 2024

Alcohols are abundant with versatile structural variety and have ample use as pivotal functional groups in numerous organic processes. Because of their frequent occurrence enumerable natural products, bioactive molecules, medicinal components, alcohol functionalities provide a promising scope research to advance the operational diversity for improving clinical success. Recent years witnessed design modern C–C C–heteroatom bond-forming approaches easily accessible commercially available unactivated aliphatic alcohols native adaptive sp3 handles, hence offering groundbreaking transformative pathways functionalization complex molecular architectures. The judicial application appropriate activating generate alkyl radical from through C–O bond fragmentation employ it potential alkylating agent unfolds unique synthetic strategies, thereby replacing obvious requirement halides. This review elaborately discusses recent trends regarding using C(sp3)-centered various chemical transformations by exploiting different activation modes disrupter under photoredox catalysis. presentation is organized nature scaffolds, kind formation, progress achieved this domain since original discovery providing illustrative examples mechanistic details, focus on difficulties future prospects.

Language: Английский

Citations

8
Radical acylation: concepts, synthetic applications and directions DOI
Yue Zhang, Yili Zhang, Jian Lin

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(4), P. 1056 - 1085

Published: Jan. 1, 2023

In this tutorial, reaction scopes, limitations and mechanisms of radical acylations are summarized discussed according to types catalytic systems.

Language: Английский

Citations

20
The most common linkers in bioactive molecules and their bioisosteric replacement network DOI
Peter Ertl, Eva Altmann, Sophie Racine

et al.

Bioorganic & Medicinal Chemistry, Journal Year: 2023, Volume and Issue: 81, P. 117194 - 117194

Published: Feb. 2, 2023

Language: Английский

Citations

20
Chemical and Redox Noninnocence of Pentane-2,4-dione Bis(S-methylisothiosemicarbazone) in Cobalt Complexes and Their Application in Wacker-Type Oxidation DOI Creative Commons
Vincent Porte, Miljan N. M. Milunović,

Ulrich Knof

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(3), P. 1166 - 1183

Published: March 12, 2024

Cobalt complexes with multiproton- and multielectron-responsive ligands are of interest for challenging catalytic transformations. The chemical redox noninnocence pentane-2,4-dione bis(S-methylisothiosemicarbazone) (PBIT) in a series cobalt has been studied by range methods, including spectroscopy [UV–vis, NMR, electron paramagnetic resonance (EPR), X-ray absorption (XAS)], cyclic voltammetry, diffraction, density functional theory (DFT) calculations. Two [CoIII(H2LSMe)I]I [CoIII(LSMe)I2] were found to act as precatalysts Wacker-type oxidation olefins using phenylsilane, the role which was elucidated through isotopic labeling. Insights into mechanism transformation well substrate scope this selective reaction described, essential phenylsilane PBIT disclosed. Among several relevant species characterized an unprecedented Co(III) complex dianionic diradical ligand ([CoIII(LSMe••)I]).

Language: Английский

Citations

7