Solvent-controlled stereodivergent synthesis of E- and Z-enamines via metal-free formal C(sp2)-H amination of α-substituted styrenes DOI Creative Commons
Dangui Wang,

Jinbei Yao,

Wentao Zhang

et al.

Green Synthesis and Catalysis, Journal Year: 2023, Volume and Issue: 5(4), P. 324 - 328

Published: Nov. 14, 2023

C(sp2)-H amination represents an attractive approach for the synthesis of enamines, which is intrinsically associated with challenge controlling stereochemistry and primarily relying on transition-metal catalysis. Herein, a metal-free α-substituted styrenes has been achieved, leading to stereodivergent formation both E- Z-enamines in 50%∼97% yield under mild conditions by using PhI(OAc)2 as green oxidant ortho-phenylenediamines nitrogen source. Interestingly, Z/E selectivity can be controlled readily switching reaction medium. E-isomers were formed preferentially THF, whereas n-hexane favored Z-isomers. Preliminary mechanistic studies suggested that situ ortho-benzoquinone diimides are key intermediates, there correlation between solvent polarity stereoselectivity. This study enriches chemical repertoire particularly respect sustainable amination.

Language: Английский

Additive-free oxidation of isochromans with molecular oxygen synergistically catalyzed by mixed-addendum polyoxometalate-based coordination polymers DOI

Zou-Guang Han,

Ling-Ling Dai,

Hongrui Tian

et al.

Rare Metals, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 28, 2025

Language: Английский

Citations

0
Expanding the Promiscuity of a Copper‐Dependent Oxidase for Enantioselective Cross‐Coupling of Indoles DOI
Huan Guo,

Ningning Sun,

Juan Guo

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(16)

Published: Feb. 15, 2023

Herein, we disclose the highly enantioselective oxidative cross-coupling of 3-hydroxyindole esters with various nucleophilic partners as catalyzed by copper efflux oxidase. The biocatalytic transformation delivers functionalized 2,2-disubstituted indolin-3-ones excellent optical purity (90-99 % ee), which exhibited anticancer activity against MCF-7 cell lines, shown preliminary biological evaluation. Mechanistic studies and molecular docking results suggest formation a phenoxyl radical enantiocontrol facilitated suited enzyme chiral pocket. This study is significant regard to expanding catalytic repertoire natural multicopper oxidases well enlarging synthetic toolbox for sustainable asymmetric coupling.

Language: Английский

Citations

8
Recent advances in catalytic oxidative reactions of phenols and naphthalenols DOI
Muhammad Adnan Bashir, Jian Wei, Huifei Wang

et al.

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(19), P. 5395 - 5413

Published: Jan. 1, 2022

This critical review aims to provide an overview of oxidative phenol and naphthalenol transformations in nature synthetic chemistry.

Language: Английский

Citations

14
Electrochemical Oxidative (4 + 2) Cyclization of Anilines and o-Phenylenediamines for the Synthesis of Phenazines DOI
Peng‐Fei Huang,

Jia-Le Fu,

Ying Peng

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(18), P. 3756 - 3761

Published: April 28, 2024

Phenazines, crucial constituents of nitrogen-containing heterocycles, widely exist in functional compounds. Herein, we report an anodic oxidative (4 + 2) cyclization between anilines and

Language: Английский

Citations

1
Visible-Light-Enabled Lanthanum-Mediated Intramolecular Epoxy-Ring Opening/Dehydrogenative Lactonization DOI
Lina Cai,

Qihong Lai,

Lele Zhang

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(39), P. 7126 - 7131

Published: Sept. 27, 2023

Catalytic C(sp3)–H functionalization has afforded great opportunities to prepare organic substances, facilitating the derivatization of complex drugs and natural molecules. This letter describes an efficient practical protocol for lanthanum-catalyzed continuous epoxy-ring opening oxidative dehydrogenative lactonization under visible-light irradiation. Notably, lanthanum catalyst also acts as a photocatalyst while acting Lewis acid in this reaction; therefore, no additional is required. We can conveniently series diverse isochromanones with oxygen-containing spirocyclic structural units balloon-oxygen atmosphere at room temperature. Mechanistic studies control experiments reveal that situ-generated bromide should be crucial reaction.

Language: Английский

Citations

3
Construction of Isochromanones via Hemin-Catalyzed Phenol-Enamine Oxidative Annulation DOI
Muhammad Adnan Bashir, Tie Wang, Hui Guo

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(24), P. 18640 - 18648

Published: Nov. 26, 2024

We have developed a hemin-catalyzed biomimetic oxidative annulation of 2,3-dihydroxybenzoic acid with an array cyclic enamines to form isochromanones in good excellent yields and high regioselectivity. This formal [4+2] cycloaddition protocol showed efficiency remarkable functional group tolerance. Mechanistic studies indicate the involvement single-electron oxidation pathway. Preliminary biological investigations that 3ag 3ca exhibited antineoplastic activities against MCF-7 cell lines IC50 values 25.21 29.09 μM, respectively.

Language: Английский

Citations

0
Expanding the Promiscuity of a Copper‐Dependent Oxidase for Enantioselective Cross‐Coupling of Indoles DOI
Huan Guo,

Ningning Sun,

Juan Guo

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(16)

Published: Feb. 15, 2023

Abstract Herein, we disclose the highly enantioselective oxidative cross‐coupling of 3‐hydroxyindole esters with various nucleophilic partners as catalyzed by copper efflux oxidase. The biocatalytic transformation delivers functionalized 2,2‐disubstituted indolin‐3‐ones excellent optical purity (90–99 % ee ), which exhibited anticancer activity against MCF‐7 cell lines, shown preliminary biological evaluation. Mechanistic studies and molecular docking results suggest formation a phenoxyl radical enantiocontrol facilitated suited enzyme chiral pocket. This study is significant regard to expanding catalytic repertoire natural multicopper oxidases well enlarging synthetic toolbox for sustainable asymmetric coupling.

Language: Английский

Citations

0
Solvent-controlled stereodivergent synthesis of E- and Z-enamines via metal-free formal C(sp2)-H amination of α-substituted styrenes DOI Creative Commons
Dangui Wang,

Jinbei Yao,

Wentao Zhang

et al.

Green Synthesis and Catalysis, Journal Year: 2023, Volume and Issue: 5(4), P. 324 - 328

Published: Nov. 14, 2023

C(sp2)-H amination represents an attractive approach for the synthesis of enamines, which is intrinsically associated with challenge controlling stereochemistry and primarily relying on transition-metal catalysis. Herein, a metal-free α-substituted styrenes has been achieved, leading to stereodivergent formation both E- Z-enamines in 50%∼97% yield under mild conditions by using PhI(OAc)2 as green oxidant ortho-phenylenediamines nitrogen source. Interestingly, Z/E selectivity can be controlled readily switching reaction medium. E-isomers were formed preferentially THF, whereas n-hexane favored Z-isomers. Preliminary mechanistic studies suggested that situ ortho-benzoquinone diimides are key intermediates, there correlation between solvent polarity stereoselectivity. This study enriches chemical repertoire particularly respect sustainable amination.

Language: Английский

Citations

0