Chemoselective Quinoline and Isoquinoline Reduction by Energy Transfer Catalysis Enabled Hydrogen Atom Transfer DOI

De‐Hai Liu,

Kyogo Nagashima,

Hui Liang

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(48)

Published: Oct. 7, 2023

Abstract (Hetero)arene reduction is one of the key avenues for synthesizing related cyclic alkenes and alkanes. While catalytic hydrogenation Birch are two broadly utilized approaches (hetero)arene across academia industry over last century, both methods have encountered significant chemoselectivity challenges. We hereby introduce a highly chemoselective quinoline isoquinoline protocol operating through selective energy transfer (EnT) catalysis, which enables subsequent hydrogen atom (HAT). The design this bypasses conventional metric reaction, that is, reductive potential, instead relies on triplet energies chemical moieties kinetic barriers events. Many reducing labile functional groups, were incompatible with previous reactions, retained in reaction. anticipate will trigger further advancement arene enable current arene‐rich drug space to escape from flatland.

Language: Английский

Radical relay cyclization/C–C bond formation of allyloxy-tethered aryl iodides with quinoxalin-2(1H)-ones via polysulfide anion photocatalysis DOI
Zhongyi Zhang, Yaqin Zhou, Jiehui Wang

et al.

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(8), P. 1708 - 1713

Published: Jan. 1, 2024

A visible-light-induced radical relay cyclization/C-C bond formation of quinoxalin-2(1

Language: Английский

Citations

26
Recent Advances in Dearomative Partial Reduction of Benzenoid Arenes DOI

De‐Hai Liu,

Jiajia Ma

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(21)

Published: March 14, 2024

Abstract Dearomative partial reduction is an extraordinary approach for transforming benzenoid arenes and has been well‐known many decades, as exemplified by the dehydrogenation of Birch hydroarylation Crich addition. Despite its remarkable importance in synthesis, this field experienced slow progress over last half‐century. However, a revival observed with recent introduction electrochemical photochemical methods. In Minireview, we summarize advancements dearomative arenes, including dihydrogenation, hydroalkylation, arylation, alkenylation, amination, borylation others. Further, intriguing utilization synthesis natural products also emphasized. It anticipated that Minireview will stimulate further arene transformations.

Language: Английский

Citations

14
Chemoselective Quinoline and Isoquinoline Reduction by Energy Transfer Catalysis Enabled Hydrogen Atom Transfer DOI

De‐Hai Liu,

Kyogo Nagashima,

Hui Liang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(48)

Published: Oct. 7, 2023

(Hetero)arene reduction is one of the key avenues for synthesizing related cyclic alkenes and alkanes. While catalytic hydrogenation Birch are two broadly utilized approaches (hetero)arene across academia industry over last century, both methods have encountered significant chemoselectivity challenges. We hereby introduce a highly chemoselective quinoline isoquinoline protocol operating through selective energy transfer (EnT) catalysis, which enables subsequent hydrogen atom (HAT). The design this bypasses conventional metric reaction, that is, reductive potential, instead relies on triplet energies chemical moieties kinetic barriers events. Many reducing labile functional groups, were incompatible with previous reactions, retained in reaction. anticipate will trigger further advancement arene enable current arene-rich drug space to escape from flatland.

Language: Английский

Citations

17
Dearomative dimerization of quinolines and their skeletal rearrangement to indoles triggered by single-electron transfer DOI

Eugene Yew Kun Tan,

Alireza Dehdari,

Amirah S. Mat Lani

et al.

Chem, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 1, 2024

Language: Английский

Citations

5
Photoredox dearomative β-hydroborylation of indoles for the synthesis of borylated indolines DOI

Yongchan Jian,

Fei Wen, Jianping Shang

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 11(1), P. 149 - 155

Published: Nov. 15, 2023

A photocatalysed dearomative β-hydroborylation reaction of indoles and NHC-boranes was developed for the construction borylated indolines.

Language: Английский

Citations

9
p-Diarylboryl Halothiophenols as Multifunctional Catalysts via Photoactive Intramolecular Frustrated Lewis Pairs DOI

Takeru Kikura,

Y. B. Taura,

Yoshitaka Aramaki

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(29), P. 20425 - 20431

Published: July 8, 2024

p-Diarylboryl halothiophenols are developed and unequivocally characterized. Their photophysical properties catalytic performance unveiled by experimental theoretical investigations. This novel class of triarylboranes behaves as a Brønsted acid to generate the corresponding borylthiophenolate that can absorb visible light undergo intramolecular charge transfer form radical pair consisting boron anion thiyl radical, which acts single-electron reductant while engaging in hydrogen atom regenerate parent borylthiophenol. The synthetic relevance this mode action is demonstrated establishment unique catalysis integrates three different yet tunable functions single cycle, thereby allowing borylthiophenols solely promote assembly sterically congested 1,2-diols 1,2-aminoalcohol derivatives via radical–radical cross-coupling.

Language: Английский

Citations

3
Excited-state protonation and reduction enables the umpolung Birch reduction of naphthalenes DOI Creative Commons
Javier Corpas, Eva Rivera‐Chao, Enrique M. Arpa

et al.

Chem, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 1, 2024

Language: Английский

Citations

3
Dearomative dimerization of quinolines and their skeletal rearrangement to indoles triggered by single-electron transfer DOI Creative Commons

Eugene Yew Kun Tan,

Alireza Dehdari,

Amirah S. Mat Lani

et al.

Published: May 29, 2024

Dearomatization of two-dimensional (2D) planar aromatic feedstocks enables the introduction three-dimensional (3D) vectors to new molecular scaffolds, vastly expanding chemical space for drug discovery. Here, we demonstrate that photoinduced single-electron reduction quinolines under polysulfide anion photocatalysis triggers dearomative dimerization and an unprecedented skeletal rearrangement. In presence excess formate as stoichiometric reductant, a complex polyheterocyclic hybrid 2,5-methanobenzo[b]azepine tetrahydroisoquinoline is formed in net-reductive manner, whereas trialkylamine instead formate, sequential rearrangement occurs afford 4-(3-indolylmethyl)quinolines redox-neutral manner. The remarkable way which additive dictates reaction course showcases unique tunability mediated redox photocatalysis. These observations enabled design 4-arylquinolines 3-(arylmethyl)indoles. Detailed mechanistic investigations reveal this umpolung transformation from electron-deficient electron-rich indoles via 1,2-aryl migration/ring-contraction sequence, opposed more commonly invoked neophyl-like

Language: Английский

Citations

1
Dearomative dimerization of quinolines and their skeletal rearrangement to indoles triggered by single-electron transfer DOI Creative Commons

Eugene Yew Kun Tan,

Alireza Dehdari,

Amirah S. Mat Lani

et al.

Published: May 29, 2024

Dearomatization of two-dimensional (2D) planar aromatic feedstocks enables the introduction three-dimensional (3D) vectors to new molecular scaffolds, vastly expanding chemical space for drug discovery. Here, we demonstrate that photoinduced single-electron reduction quinolines under polysulfide anion photocatalysis triggers dearomative dimerization and an unprecedented skeletal rearrangement. In presence excess formate as stoichiometric reductant, a complex polyheterocyclic hybrid 2,5-methanobenzo[b]azepine tetrahydroisoquinoline is formed in net-reductive manner, whereas trialkylamine instead formate, sequential rearrangement occurs afford 4-(3-indolylmethyl)quinolines redox-neutral manner. The remarkable way which additive dictates reaction course showcases unique tunability mediated redox photocatalysis. These observations enabled design 4-arylquinolines 3-(arylmethyl)indoles. Detailed mechanistic investigations reveal this umpolung transformation from electron-deficient electron-rich indoles via 1,2-aryl migration/ring-contraction sequence, opposed more commonly invoked neophyl-like

Language: Английский

Citations

1
Dearomative dimerization of quinolines and their skeletal rearrangement to indoles triggered by single-electron transfer DOI Creative Commons

Eugene Yew Kun Tan,

Alireza Dehdari,

Amirah S. Mat Lani

et al.

Published: May 30, 2024

Dearomatization of two-dimensional (2D) planar aromatic feedstocks enables the introduction three-dimensional (3D) vectors to new molecular scaffolds, vastly expanding chemical space for drug discovery. Here, we demonstrate that photoinduced single-electron reduction quinolines under polysulfide anion photocatalysis triggers dearomative dimerization and an unprecedented skeletal rearrangement. In presence excess formate as stoichiometric reductant, a complex polyheterocyclic hybrid 2,5-methanobenzo[b]azepine tetrahydroisoquinoline is formed in net-reductive manner, whereas trialkylamine instead formate, sequential rearrangement occurs afford 4-(3-indolylmethyl)quinolines redox-neutral manner. The remarkable way which additive dictates reaction course showcases unique tunability mediated redox photocatalysis. These observations enabled design 4-arylquinolines 3-(arylmethyl)indoles. Detailed mechanistic investigations reveal this umpolung transformation from electron-deficient electron-rich indoles via 1,2-aryl migration/ring-contraction sequence, opposed more commonly invoked neophyl-like

Language: Английский

Citations

1