Visible-Light-Induced Imine Hydrogenation Catalyzed by Thioxanthone-TfOH Complex

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 9, 2025

Amino compounds are important molecules, commonly found in nature and widely applied industrial production. Recently, photocatalysis has been discovered as an efficient method to synthesize amino by promoting imine hydrogenation. In this work, a strategy of hydrogenation catalyzed 2e– consecutive photoinduced electron transfer (ConPET) process thioxanthone-TfOH complex (9-HTXTF) was thoroughly investigated with its reaction conditions optimized, substrate scope examined, mechanism elucidated, which provides for synthesizing compounds.

Язык: Английский

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Designing Ruthenium Phthalocyanine with Chiral Pockets Formed by (1R,2S,5R)-Menthoxy Groups for Enantioselective Catalysis

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4984 - 5001

Опубликована: Март 10, 2025

Unprecedented chiral ruthenium(II) complexes with phthalocyanines having motifs near the catalytic metal site have been prepared by cross condensation of 3,6-bis-aryloxy-phthalonitrile (α-Ar*O)2Pn bearing two (1R,2S,5R)-menthoxy groups orthogonal to aromatic plane and (15-crown-5)phthalonitrile. Four containing menthyl (M) 15-crown-5 units (C), notably RuPc[MC3](CO), RuPc[opp-M2C2](CO), RuPc[adj-M2C2](CO), RuPc[M3C](CO), were isolated in pure form fully characterized UV–vis, circular dichroism, HRMS, various 1H NMR 13C techniques. Their evaluation benchmark asymmetric cyclopropanation reaction styrene derivatives ethyl diazoacetate indicated that RuPc[opp-M2C2](CO) complex was most efficient terms diastereo- enantioselectivity. Further study revealed strong dependence stereoselectivity on solvent nature salt additives, which caused conformational rearrangement flexible surrounding, as evidenced multinuclear CD spectra. For instance, upon moving from commonly used CH2Cl2 EtOH addition NaPF6, a significant enhancement enantioselectivity (from 35 84% p-methylstyrene) obtained. Of particular importance is very high diastereoselectivity many substrates promoted incorporation sodium cations into crown ether cavities phthalocyanine attain trans/cis ratio up 499:1. Such regulating effect catalysis involving tetrapyrrolic has not previously observed, rendering this prominent example tunable catalyst. The developed synthetic strategy paves way environment around receptors tune properties.

Язык: Английский

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Catalytic acceptorless dehydrogenation of alcohols using cobalt(i) pincer complexes supported by a P–GeH–P ligand

Chemical Communications, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

We report a novel P–GeH–P pincer ligand and its cobalt( i ) complex, which catalyzes the acceptorless dehydrogenation of alcohols.

Язык: Английский

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In₂S₃‐BaTiO₃ S‐Type Heterojunction Photocatalyst for Efficient Antibiotic Degradation and Hydrogen Generation

Small, Год журнала: 2025, Номер unknown

Опубликована: Апрель 24, 2025

Abstract Quinolone antibiotics, particularly moxifloxacin (MOX), are increasingly contaminating aquatic ecosystems, posing significant threats to both the environment and human health. Due its hydrophilicity stability, traditional water treatment methods ineffective in degrading MOX. In this study, a novel S‐type heterojunction photocatalyst, In‐Ba‐10, is introduced which combines barium titanate (BaTiO 3 ) indium sulfide (In 2 S address challenge. The In‐Ba‐10 catalyst demonstrates excellent photocatalytic performance, with hydrogen production rate of 2050 µmol g −1 h MOX degradation constant (k) 0.049 min . Compared BaTiO alone, performance enhanced by 48‐ 49‐fold, respectively. Comprehensive characterization, including Raman spectroscopy, X‐ray photoelectron spectroscopy (XPS), electron microscopy, reveals that effectively promotes charge separation transfer, reduces electron–hole recombination, improves catalytic efficiency. First‐principles calculations further confirm role as reduction site oxidation site. addition high activity, ‐BaTiO shows stability over multiple cycles, making it promising candidate for sustainable wastewater treatment. This study highlights potential photocatalysts environmental remediation energy applications.

Язык: Английский

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Enantioselective Nitrene Transfer to Hydrocinnamyl Alcohols and Allylic Alcohols Enabled by Systematic Exploration of the Structure of Ion-Paired Rhodium Catalysts

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(32), С. 22629 - 22641

Опубликована: Июль 31, 2024

This work describes highly enantioselective nitrene transfer to hydrocinnamyl alcohols (benzylic C–H amination) and allylic (aziridination) using ion-paired Rh (II,II) complexes based on anionic variants of Du Bois' esp ligand that are associated with cinchona alkaloid-derived chiral cations. Directed by a substrate hydroxyl group, our previous these had not been able achieve high enantioselectivity most useful short-chain compounds, we overcame this challenge through combination catalyst design modified conditions. A hypothesis modulation the linker between sulfonate group central arene spacer might provide better fit for shorter chain length substrates led development new biaryl-containing scaffold, which has allowed broad scope both classes be realized first time. Furthermore, describe systematic structural "knockout" study cation elucidate features crucial enantioinduction. De novo synthesis scaffolds surprising finding ee quinoline nitrogen alkaloid is crucial, although its location within heterocycle could varied, even leading superior catalyst. The free also should possess naturally occurring diastereomeric configuration alkaloid. These findings underline privileged nature scaffold insight into how cations used in other catalysis contexts.

Язык: Английский

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Intramolecular Cobalt Porphyrin-Catalyzed Alkylation of 1-Isoindolinones by Site-Selective Insertion into a C(sp³)–H Bond

Organic Letters, Год журнала: 2024, Номер 26(35), С. 7302 - 7306

Опубликована: Авг. 27, 2024

1-Isoindolinones with a reactive hydrazone tether attached to the nitrogen atom underwent an intramolecular alkylation in presence of cobalt(tetraphenylporphyrin) and base. Products display saturated heterocyclic rings various sizes (

Язык: Английский

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