Asymmetric arene hydrogenation: towards sustainability and application

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(15), P. 4996 - 5012

Published: Jan. 1, 2023

This review summarises the state-of-the-art in transition-metal catalysed asymmetric hydrogenation of (hetero)arenes and highlights recent advances with a special focus on sustainability while also addressing its shortcomings.

Language: Английский

---

Enantioselective Synthesis of Chiral 1,4-Dihydroquinolines via Iridium-Catalyzed Asymmetric Partial Hydrogenation of Quinolines

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 5, 2025

Chiral 1,4-dihydroquinolines are frequently found in natural products and pharmaceuticals, yet a generally useful route for their synthesis remains elusive. Here, we present an asymmetric partial hydrogenation strategy to access enantioenriched from quinolines. Our involves incorporating ester group at position 3 of the quinoline ring, thereby enhancing electronic deficiency polarity C3–C4 double bond. Employing chiral Ir-SpiroPAP catalyst facilitated wide variety 4-substituted 3-ethoxycarbonylquinolines, yielding high yields (up 95%) with exceptional enantioselectivity efficiency 99% ee 1840 TONs). Noteworthy its scalability practicality, method provides robust avenue valuable compounds such as 9-aryl aza-podophyllotoxins melatonin MT2 receptor modulators. Density functional theory calculations were performed gain insights into reaction mechanism origins enantioselectivity.

Language: Английский

---

Dynamic Kinetic Resolution-Based Asymmetric Transfer Hydrogenation of Racemic 2-Substituted Quinolines

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 22, 2025

The synthesis of chiral tetrahydroquinolines (THQs) has garnered significant interest from medicinal chemists due to their frequent presence as pharmacophores in bioactive compounds. While existing synthetic methods have primarily focused on THQs with single or multiple endocyclic centers, the selective construction both endo- and exo-cyclic centers remains a challenge that requires further development. This study introduces dynamic kinetic resolution (DKR)-based transfer hydrogenation racemic 2-substituted quinolines, which yields structurally novel consecutive excellent stereoselectivities (59 examples, generally >20:1 dr >90% ee, up three stereocenters). Our approach offers mechanistically method for asymmetric transformation electron-deficient aromatic N-heterocycles presents an innovative way expand N-heterocycle chemical space chemistry.

Language: Английский

---

Recent advances of Cp*Ir complexes for transfer hydrogenation: focus on formic acid/formate as hydrogen donors

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(37), P. 7484 - 7497

Published: Jan. 1, 2023

This review summarise the transfer hydrogenation of C=O, C=C, C=N bonds unsaturated substrates via Cp*Ir complexes as catalysts and formic acid/formate hydrogen sources.

Language: Английский

---

Transition Metal Complexes with Amino Acids, Peptides and Carbohydrates in Catalytic Asymmetric Synthesis: A Short Review

Processes, Journal Year: 2024, Volume and Issue: 12(1), P. 214 - 214

Published: Jan. 18, 2024

The present review is devoted to the application of transition metal complexes with such ligands as amino acids, peptides and carbohydrates in catalysis. literature published over past 20 years surveyed. Among distinctive features these are their versatility, optical activity, stability availability. Furthermore, depending on specific synthetic task be solved, open up almost infinite opportunity for modification. Largely thanks multifaceted reactivity, can catalyze most known chemical reactions affording optically pure compounds. In this review, emphasis placed upon C(sp3)–H activation, cross-coupling hydrogenation (including traditional presence hydrogen gas transfer) reactions. choice not accidental, since one hand display catalytic versatility above complexes, other hand, they widely employed industry.

Language: Английский

---

Transfer hydrogenation of pyridinium and quinolinium species using ethanol as a hydrogen source to access saturated N-heterocycles

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(26), P. 4255 - 4258

Published: Jan. 1, 2022

Catalytic transfer hydrogenation (TH) for the reduction of heterocycles is an emerging strategy accessing biologically active saturated N-heterocycles. Herein, we report a TH protocol that utilizes ethanol as renewable hydrogen source and Ir catalyst quinolines pyridines. The reaction promoted by simple amides ligands.

Language: Английский

---

Asymmetric Reduction of Quinolines: A Competition between Enantioselective Transfer Hydrogenation and Racemic Borane Catalysis

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(5), P. 3335 - 3339

Published: Feb. 17, 2023

A chiral phosphoric acid catalyzed asymmetric transfer hydrogenation of quinolines with regenerable dihydrophenanthridine derived by a borane-catalyzed phenanthridine under H2 has been successfully realized. Despite the competition racemic pathway, variety tetrahydroquinolines were furnished in high yields up to 91% ee.

Language: Английский

---

Manganese-catalyzed asymmetric transfer hydrogenation of quinolines in water using ammonia borane as a hydrogen source

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(10), P. 5933 - 5939

Published: Jan. 1, 2024

The first example of manganese-catalyzed asymmetric transfer hydrogenation N-heteroaromatics in water with good yields and ee up to 99%.

Language: Английский

---

A recyclable rhodium catalyst anchored onto a bipyridine covalent triazine framework for transfer hydrogenation of N-heteroarenes in water

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(8), P. 3267 - 3277

Published: Jan. 1, 2023

Bipyridine covalent triazine framework (bpyCTF) was used as a support material for the development of highly efficient Rh catalyst. The heterogeneous catalyst applied both batch and flow transfer hydrogenation various N-heteroarenes.

Language: Английский

---

Synthesis and Characterization of Chiral Iridium Complexes Bearing Carbohydrate Functionalized Pyridincarboxamide Ligands and Their Application as Catalysts in the Asymmetric Transfer Hydrogenation of α-Ketoacids in Water

Organometallics, Journal Year: 2023, Volume and Issue: 42(2), P. 157 - 166

Published: Jan. 5, 2023

[Cp*IrLnCl] complexes [L1 = (methyl-β-d-glucopyranosid-2-yl)picolinamide, 1; L2 (methyl-3,4,6-tri-O-acetyl-β-d-glucopyranosid-2-yl)picolinamide, 2; L3 (2,3,4,6-tetra-O-acetyl-β-d-glucopyranosid-1-yl)picolinamide, 3] have been synthesized and completely characterized in solution, by 1D- 2D-NMR spectroscopy, the solid state, X-ray single crystal diffractometry. Despite chirality of Ln-moiety metal, a diastereoisomer is observed for L1 (1) (2) having (R)-iridium configuration: pyranose moiety oriented way to minimize interactions axial protons, vicinal amide moiety, Cp*, with OMe-group pointing toward Cp*-ligand away from Ir–Cl. Such also favored establishment an O–H···Cl–Ir hydrogen bond (2.356 Å) minimization steric repulsion between one acetyl Cp* picolinamide ligands 1 2, respectively. DFT calculations computed stabilization more than 5.9 3.1 kcal/mol this respect other possible ones. Two interconverting diastereoisomers different at iridium are instead solution complex 3 which −CH2OAc [3a, 63%, (R)] −OAc [3b, 37%, (S)] moieties, respectively, N-arm ligands. Consistently, indicate that 3a 3b comparable stability (ΔE 1.2 kcal/mol). Complexes 1–3 catalyze asymmetric transfer hydrogenation RC(O)C(O)OH RCH(OH)C(O)OH [R Ph (PGA), CH2Ph (PPA), CH2(4-OH)C6H4 (HPPA)], using both HCOOH H3PO3 as donor, water pH 7 (by phosphate buffer), excellent chemoselectivity efficiency (conversion >99%) moderate good enantioselectivity (30–70% ee). Utilizing catalyst bearing pseudoenantiomeric ligand, causes reduction percentage major enantiomer (R) PGA inversion stereoselectivity (S) PPA HPPA substrates.

Language: Английский

---