Modular and Practical 1,2‐Aryl(Alkenyl) Heteroatom Functionalization of Alkenes through Iron/Photoredox Dual Catalysis**

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(44)

Published: Sept. 13, 2023

Abstract Efficient methods for synthesizing 1,2‐aryl(alkenyl) heteroatomic cores, encompassing heteroatoms such as nitrogen, oxygen, sulfur, and halogens, are of significant importance in medicinal chemistry pharmaceutical research. In this study, we present a mild, versatile practical photoredox/iron dual catalytic system that enables access to highly privileged pharmacophores with exceptional efficiency site selectivity. Our approach exhibits an extensive scope, allowing the direct utilization wide range commodity or commercially available (hetero)arenes well activated unactivated alkenes diverse functional groups, drug scaffolds, natural product motifs substrates. By merging iron catalysis photoredox cycle, vast array alkene functionalization products incorporate neighboring azido, amino, halo, thiocyano nitrooxy group were secured. The scalability ability rapid synthesize numerous bioactive small molecules from readily starting materials highlight utility protocol.

Language: Английский

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Exploiting π and Chalcogen Interactions for the β‐Selective Glycosylation of Indoles through Glycal Conformational Distortion

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(7)

Published: Dec. 20, 2023

Harnessing unconventional noncovalent interactions (NCIs) is emerging as a formidable synthetic approach in difficult-to-access glycosidic chemical space. C-Glycosylation, particular, has gained flurry of recent attention. However, most reported methods are restricted to the relatively facile access α-C-glycosides. Herein, we disclose β-stereoselective glycosylation indoles by employing phosphonoselenide catalyst. The robustness this protocol exemplified its amenability for reaction at both indolyl C- and N- reactivity sites. In contrast previous reports, which chalcogens were solely involved Lewis acidic activation, our mechanistic investigation unraveled that often neglected flanking aromatic substituents phosphonoselenides can substantially contribute catalysis engaging π-interactions. Computations NMR spectroscopy indicated chalcogenic components catalyst be collectively exploited foster conformational distortion glycal away from usual half-chair boat conformation, liberates convex β-face nucleophilic attack.

Language: Английский

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Zirconaaziridine-Mediated Ni-Catalyzed Diastereoselective C(sp²)-Glycosylation

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(24), P. 16753 - 16763

Published: June 11, 2024

In the realm of organic synthesis, catalytic and stereoselective formation C-glycosidic bonds is a pivotal process, bridging carbohydrates with aglycones. However, inherent chirality saccharide scaffold often has substantial impact on stereoinduction imposed by chiral ligand. this study, we have established an unprecedented zirconaaziridine-mediated asymmetric nickel catalysis, enabling diastereoselective coupling bench-stable glycosyl phosphates range (hetero)aromatic glycal iodides as feasible electrophiles. Our developed method showcases broad scope high tolerance for various functional groups. More importantly, precise stereocontrol toward both anomeric configurations forming C(sp2)-glycosides can be realized simply utilizing popular bioxazoline (biOx) ligands in reductive Ni catalysis. Regarding operating mechanism, experimental computational studies support occurrence redox transmetalation leading to transient, bimetallic Ni–Zr species that acts potent efficient single-electron reductant process.

Language: Английский

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Recent Advances on Natural Aryl-C-glycoside Scaffolds: Structure, Bioactivities, and Synthesis—A Comprehensive Review

Molecules, Journal Year: 2022, Volume and Issue: 27(21), P. 7439 - 7439

Published: Nov. 1, 2022

Aryl-C-glycosides, of both synthetic and natural origin, are great significance in medicinal chemistry owing to their unique structures stability towards enzymatic chemical hydrolysis as compared O-glycosides. They well-known antibiotics potent enzyme inhibitors possess a wide range biological activities such anticancer, antioxidant, antiviral, hypoglycemic effects, so on. Currently, number aryl-C-glycoside drugs on sale for the treatment diabetes related complications. This review summarizes findings scaffolds over past 20 years, concerning new (over 200 molecules), bioactivities—including anti-inflammatory, antivirus, glycation inhibitory other pharmacological effects—as well synthesis.

Language: Английский

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Synthesis of 2-Indolyl C-Glycoside Neopetrosins A and C and Congeners via Ni-Catalyzed Photoreductive Cross-Coupling

Organic Letters, Journal Year: 2023, Volume and Issue: 25(36), P. 6741 - 6745

Published: Aug. 30, 2023

The synthesis of neopetrosins A and C, two 2-indolyl C-α-d-mannopyranosides, their congeners has been realized via a direct Ni/photoredox-catalyzed reductive coupling 3-methoxycarbonyl-2-iodo-1H-indoles with pyranosyl bromides.

Language: Английский

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