Construction of Chiral C2-Quaternary Indolines via Palladium-Catalyzed Decarboxylative Asymmetric Amination DOI

Mingjun Lv,

Xinhui Yu,

Jitian Liu

и другие.

ACS Catalysis, Год журнала: 2024, Номер 15(1), С. 255 - 264

Опубликована: Дек. 16, 2024

The catalytic asymmetric synthesis of functionalized C2-quaternary indoline scaffolds has garnered significant attention in organic and drug discovery due to the inherent challenges potential applications. Herein, we present a facile approach utilizing Pd-catalyzed intramolecular decarboxylative amination vinyl benzoxazepinones, leading efficient construction challenging chiral 2-vinyl-2-aryl/alkyl frameworks good yields with high enantioselectivities (>50 examples, up 83% yield 97% ee). Furthermore, these indolines can be readily scaled further modified access complex polycyclic structures. We also synthesized several indoline-based ligands that exhibit promising efficiency as catalysts reactions. Computational studies provided insight into inner-sphere mechanism.

Язык: Английский

Dynamic Kinetic Resolution-Based Asymmetric Transfer Hydrogenation of Racemic 2-Substituted Quinolines DOI
Liang Meng,

Xian Du,

Jian Jun Lin

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 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.

Язык: Английский

Процитировано

1

A meta-learning approach for selectivity prediction in asymmetric catalysis DOI Creative Commons
Sukriti Singh, José Miguel Hernández-Lobato

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Апрель 15, 2025

Abstract Transition metal-catalyzed asymmetric reactions are of high contemporary importance in organic synthesis. Recently, machine learning (ML) has shown promise accelerating the development newer catalytic protocols. However, need for large amount experimental data can present a bottleneck implementing ML models. Here, we propose meta-learning workflow that harness literature-derived to extract shared reaction features and requires only few examples predict outcome new reactions. Prototypical networks used as method enantioselectivity hydrogenation olefins. This model consistently provides significant performance improvement over other popular methods such random forests graph neural networks. The our meta-model is analyzed with varying sizes training demonstrate its utility even limited data. A good on an out-of-sample test set further indicates general applicability approach. We believe this work will provide leap forward identifying promising early phases when minimal available.

Язык: Английский

Процитировано

0

Iridium-Catalyzed Asymmetric Hydrogenation of Unfunctionalized Cycloalkenes to Access Chiral 2-Aryl Tetralins DOI

Tierui Pan,

Qianjia Yuan, Defeng Xu

и другие.

Organic Letters, Год журнала: 2024, Номер 26(27), С. 5850 - 5855

Опубликована: Июль 1, 2024

The transition-metal catalyzed asymmetric hydrogenation of unfunctionalized alkenes is challenging. Herein, we report an efficient iridium-catalyzed cycloalkenes, delivering chiral 2-aryl tetralins in excellent yields and with moderate to enantioselectivities. reaction can be performed on a gram-scale low catalyst loading (S/C = 1000), the reduced product was obtained without erosion enantioselectivity. Deuterium experiments indicated that C═C bond substrate hydrogenated directly isomerization.

Язык: Английский

Процитировано

1

Synthesis and applications of optically pure trans-2-(3,5-dimethylphenoxy)cyclohexan-1-ol as chiral auxiliary for preparation of α-substituted carboxylic acid derivatives DOI

Atul R. Pandavadara,

Aditya N. Khanvilkar,

Ashutosh V. Bedekar

и другие.

Tetrahedron, Год журнала: 2024, Номер unknown, С. 134326 - 134326

Опубликована: Окт. 1, 2024

Язык: Английский

Процитировано

1

Enantioselective Synthesis of Chiral β2-Amino Phosphorus Derivatives via Nickel-Catalyzed Asymmetric Hydrogenation DOI

Hanlin Wei,

Yicong Luo, Jinhui Li

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Дек. 27, 2024

Compared with chiral β3-amino phosphorus compounds, which can be easily derived from natural optically pure α-amino acids, obtaining β2-amino derivatives remains a challenge. These derivatives, cannot amino possess unique biological activities or potential catalytic activities. Herein, highly enantioselective hydrogenation for the preparation of E-β-enamido compounds is reported by using green and low-cost earth-abundant metal nickel catalyst (13 examples 99% ee). In particular, this system provides same enantiomer product E- Z-alkene substrates, E/Z-substrate mixtures provide good results (up to 96% The products diversely derivatized, exhibit as novel β2-aminophosphine ligands. Density functional theory calculations reveal that weak attractive interactions between substrate are crucial achieving perfect enantioselectivities. addition, different coordination modes Z-substrates may result in formation product.

Язык: Английский

Процитировано

1

A New Dynamic Kinetic Resolution Strategy for Asymmetric Hydrogenation of Indoles DOI Open Access
Tong Niu, Yong‐Gui Zhou

Chinese Journal of Organic Chemistry, Год журнала: 2024, Номер 44(4), С. 1374 - 1374

Опубликована: Янв. 1, 2024

Язык: Английский

Процитировано

0

Dynamic Kinetic Resolution of Racemic 2-Substituted Indoles by Pd-Catalyzed Asymmetric Hydrogenation DOI
Martin Oestreich, Hendrik F. T. Klare, Nektarios Kranidiotis‐Hisatomi

и другие.

Synfacts, Год журнала: 2024, Номер 20(06), С. 0604 - 0604

Опубликована: Май 14, 2024

Key words dynamic kinetic resolution - hydrogenation indoles indolines palladium catalysis vicinal stereogenic centers

Язык: Английский

Процитировано

0

Construction of Chiral C2-Quaternary Indolines via Palladium-Catalyzed Decarboxylative Asymmetric Amination DOI

Mingjun Lv,

Xinhui Yu,

Jitian Liu

и другие.

ACS Catalysis, Год журнала: 2024, Номер 15(1), С. 255 - 264

Опубликована: Дек. 16, 2024

The catalytic asymmetric synthesis of functionalized C2-quaternary indoline scaffolds has garnered significant attention in organic and drug discovery due to the inherent challenges potential applications. Herein, we present a facile approach utilizing Pd-catalyzed intramolecular decarboxylative amination vinyl benzoxazepinones, leading efficient construction challenging chiral 2-vinyl-2-aryl/alkyl frameworks good yields with high enantioselectivities (>50 examples, up 83% yield 97% ee). Furthermore, these indolines can be readily scaled further modified access complex polycyclic structures. We also synthesized several indoline-based ligands that exhibit promising efficiency as catalysts reactions. Computational studies provided insight into inner-sphere mechanism.

Язык: Английский

Процитировано

0