Ru‐NHC‐Catalyzed Asymmetric Hydrogenation of 2‐Quinolones to Chiral 3,4‐Dihydro‐2‐Quinolones DOI Creative Commons

Tianjiao Hu,

Lukas Lückemeier,

Constantin G. Daniliuc

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(43), P. 23193 - 23196

Published: Aug. 30, 2021

Direct enantioselective hydrogenation of unsaturated compounds to generate chiral three-dimensional motifs is one the most straightforward and important approaches in synthetic chemistry. We realized Ru(II)-NHC-catalyzed asymmetric 2-quinolones under mild reaction conditions. Alkyl-, aryl- halogen-substituted optically active dihydro-2-quinolones were obtained high yields with moderate excellent enantioselectivities. The provides an efficient atom-economic pathway construct simple 3,4-dihydro-2-quinolones. desired products could be further reduced tetrahydroquinolines octahydroquinolones.

Language: Английский

Substituted Dihydropyridine Synthesis by Dearomatization of Pyridines DOI Creative Commons
Arne Heusler,

Julian Fliege,

Tobias Wagener

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(25), P. 13793 - 13797

Published: April 8, 2021

Dearomatization is an effective method to transform readily available N-heterocycles into partially saturated motifs. Manipulation of dihydro-derivatives holds great potential and provides access a variety semi-saturated N-heterocyclic building blocks. However, current strategies are limited in scope the use sensitive reagents restricts applicability synthetic laboratories. Herein, we report synthesis broad N-substituted 1,4- 1,2-dihydropyridines by very mild selective reduction with amine borane for first time.

Language: Английский

Citations

38
Dearomative Aminocarbonylation of Arenes via Bifunctional Coordination to Chromium DOI Open Access
Ming‐Yang Wang,

Cheng‐Jie Wu,

Wei‐Long Zeng

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(41)

Published: Aug. 16, 2022

Abstract Amides are ubiquitous in physical and life sciences. Given the significant abundance of arenes, dearomative aminocarbonylation arenes would lead to a large underexplored chemical space for amide discovery. However, such reactions challenging due high degree resonance stabilization selectivity issues. Herein, we disclose an unprecedented trifluoromethylative via bifunctional coordination chromium, providing modular platform construction amides possessing trifluoromethyl (CF 3 ) groups three‐dimensional rings. Its versatility further enabled switchable difluoromethylation or trifluoromethylation arene C−H bonds. A possible mechanism was proposed based on control experiments. Finally, synthetic utility well demonstrated by diverse applications total synthesis CF ‐functionalized amide‐type drugs, including praziquantel, nateglinide, maraviroc alloyohimbane.

Language: Английский

Citations

23
Borane‐Catalyzed Chemoselective and Enantioselective Reduction of 2‐Vinyl‐Substituted Pyridines DOI

Jun‐Jie Tian,

Zhao‐Ying Yang,

Xin‐Shen Liang

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(42), P. 18452 - 18456

Published: July 8, 2020

Abstract Herein, we report that highly chemoselective and enantioselective reduction of 2‐vinyl‐substituted pyridines has been achieved for the first time. The reaction, which uses chiral spiro‐bicyclic bisboranes as catalysts HBpin an acidic amide reducing reagents, proceeds through a cascade process involving 1,4‐hydroboration followed by transfer hydrogenation dihydropyridine intermediate. retained double bond in products permits their conversion to natural other useful heterocyclic compounds simple transformations.

Language: Английский

Citations

37
Rhodium‐Catalyzed Asymmetric Hydrogenation of 3‐Benzoylaminocoumarins for the Synthesis of Chiral 3‐Amino Dihydrocoumarins DOI
Yunnan Xu, Delong Liu, Yu Deng

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(44), P. 23602 - 23607

Published: Oct. 1, 2021

An asymmetric hydrogenation of 3-benzoylaminocoumarins was achieved for the first time using our BridgePhos-Rh catalytic system, providing chiral 3-amino dihydrocoumarins in high yields (up to 98 %) and with excellent enantioselectivities 99.7 % ee). The relationship between hydrogenations dihedral angles resulting π-π stacking effects complexes, which were determined by X-ray diffraction analysis, are discussed. corresponding hydrogenated products allow many transformations, several skeletons important physiological pharmacological activities.

Language: Английский

Citations

30
Rhodium‐Catalyzed Asymmetric Hydrogenation of All‐Carbon Aromatic Rings DOI

Yi‐Xuan Ding,

Zhou‐Hao Zhu, Mu‐Wang Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(34)

Published: June 29, 2022

Compared with heteroarenes, homogeneous asymmetric hydrogenation of all-carbon aromatic rings is a longstanding challenge in organic synthesis due to the strong aromaticity and difficult enantioselective control. Herein, we report rhodium/diphosphine-catalyzed rings, affording series axially chiral cyclic compounds high enantioselectivity through desymmetrization or kinetic resolution. In addition, central-chiral were also obtained by phenanthrenes bearing directing group. The key success introduction diphosphine ligands steric hindrance electron-donating properties. monophosphine could be simple conversion products phosphine atom.

Language: Английский

Citations

22
Transition‐Metal‐Free Reductive Hydroxymethylation of Isoquinolines DOI Creative Commons

Benjamin M. Reeves,

Hamish B. Hepburn, Alexandru Grozavu

et al.

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(44), P. 15697 - 15701

Published: Sept. 5, 2019

Abstract A transition‐metal‐free reductive hydroxymethylation reaction has been developed, enabling the preparation of tetrahydroisoquinolines bearing C4‐quaternary centers from corresponding isoquinolines. Deuterium labelling studies and control experiments enable a potential mechanism to be elucidated which features key Cannizzaro‐type reduction followed by an Evans–Tishchenko reaction. When isoquinolines featuring proton at 4‐position are used, tandem methylation‐hydroxymethylation occurs, leading formation 2 new C−C bonds in one pot.

Language: Английский

Citations

33
Iridium‐Catalyzed Enantioselective Hydrogenation of Indole and Benzofuran Derivatives DOI
Yao Ge, Zheng Wang, Zhaobin Han

et al.

Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 26(67), P. 15482 - 15486

Published: July 2, 2020

Abstract Enantioselective hydrogenation of a broad spectrum N‐, O‐, and S‐containing aromatic benzoheterocycles or nonaromatic unsaturated heterocycles has been realized by using an Ir/SpinPHOX (SpinPHOX=spiro[4,4]‐1,6‐nonadiene‐based phosphine‐oxazoline) complex as the catalyst, affording array corresponding chiral (30 examples) with excellent enantioselectivities (>99 % ee in most cases) turnover numbers up to 500.

Language: Английский

Citations

31
Intermolecular Dearomative 1,2‐Amination/Carbonylation via Nucleophilic Addition of Simple Amines to Arene π‐Bonds DOI
Zheng Jian Li, Ming‐Yang Wang, Chuqiao Li

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(36)

Published: April 19, 2023

The incorporation of the privileged amino functionality is paramount importance in organic synthesis. In contrast to well-developed amination methods for alkenes, dearomative arenes largely underexplored due inherently inert reactivity arene π-bonds and selectivity challenges. Herein, we report an intermolecular aminofunctionalization via direct nucleophilic addition simple amines chromium-bound arenes. This multicomponent 1,2-amination/carbonylation reaction enables rapid access complicated alicyclic compounds containing amide functionalities from benzene derivatives under CO-gas-free conditions, which also represents first application nitrogen-based nucleophiles η6 -coordination-induced dearomatizations.

Language: Английский

Citations

10
Synthesis of Saturated N‐Heterocycles via a Catalytic Hydrogenation Cascade DOI Creative Commons

Tobias Wagener,

Marco Pierau,

Arne Heusler

et al.

Advanced Synthesis & Catalysis, Journal Year: 2022, Volume and Issue: 364(19), P. 3366 - 3371

Published: June 9, 2022

Saturated N-heterocycles are prominent motifs found in various natural products and pharmaceuticals. Despite the increasing interest this class of compounds, synthesis saturated bicyclic azacycles requires tedious multi-step syntheses. Herein, we present a one-pot protocol for octahydroindoles, decahydroquinolines, octahydroindolizines through cascade reaction.

Language: Английский

Citations

15
Manganese‐Catalyzed Asymmetric Hydrogenation of Quinolines Enabled by π–π Interaction** DOI
Chenguang Liu, Mingyang Wang, Shihan Liu

et al.

Angewandte Chemie, Journal Year: 2020, Volume and Issue: 133(10), P. 5168 - 5173

Published: Nov. 26, 2020

Abstract The non‐noble metal‐catalyzed asymmetric hydrogenation of N‐heteroaromatics, quinolines, is reported. A new chiral pincer manganese catalyst showed outstanding catalytic activity in the affording high yields and enantioselectivities (up to 97 % ee). turnover number 3840 was reached at a low loading (S/C=4000), which competitive with most effective noble metal catalysts for this reaction. precise regulation enantioselectivity were ensured by π–π interaction.

Language: Английский

Citations

23