Cited by NHC-Catalyzed Covalent Activation and Control of P(V)-Stereogenic Phosphorus Centers via Phosphonyl Azolium Intermediates

Catalytic Enantioselective Nucleophilic Desymmetrization at Phosphorus(V): A Three-Phase Strategy for Modular Preparation of Phosphoramidates DOI

Xiao‐kang Nie,

Shiqi Zhang, Xuyang Wang

et al.

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

Published: March 19, 2025

Chiral phosphoramidates characterized by at least a P–N bond without P–C demonstrate significant applicative value within nucleoside phosphoramidate prodrugs. Despite the availability of methodologies for selective construction diverse chiral organophosphorus entities, achieving P-stereocenters solely substituted heteroatoms often relies on diastereomeric synthesis. Here, we present catalytic enantioselective desymmetrization strategy using an electrophilic phosphorus reagent with three leaving groups as substrate, enabling three-phase nucleophilic attack various alcohols and amines. By generating broad range possible substituent combinations around atoms, this synthetic may expedite synthesis screening biologically active phosphoramidates.

Language: Английский

Citations

Enantioselective Synthesis of P-Chiral Phosphine Oxides Bearing an All-Carbon Quaternary Stereogenic Center via Palladium-Catalyzed Domino Heck–Suzuki Reaction DOI

Siyu Zhao, Jiahao Liu,

Xunfang Xu

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 14762 - 14768

Published: Sept. 20, 2024

Language: Английский

Citations

Copper‐Catalyzed Enantioselective Hydrophosphorylation of Unactivated Alkynes DOI

Jie Kang,

Kang Ding,

Si‐Mu Ren

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 5, 2024

P-stereogenic phosphorus compounds are essential across various fields, yet their synthesis via enantioselective P-C bond formation remains both challenging and underdeveloped. We report the first copper-catalyzed hydrophosphorylation of alkynes, facilitated by a newly designed chiral 1,2-diamine ligand. Unlike previous methods that rely on kinetic resolution with less than 50 % conversion, our approach employs distinct dynamic asymmetric transformation mechanism, achieving complete conversion racemic starting materials. This reaction is compatible broad range aromatic aliphatic terminal producing products high yields (up to 95 %), exclusive cis selectivity, exceptional regio- enantioselectivity (>20 : 1 r.r. up 96 ee). The resulting were further transformed into diverse array enantioenriched scaffolds. Preliminary mechanistic studies conducted elucidate details.

Language: Английский

Citations

Synthesis of P(V)-Stereogenic Phosphorus Compounds via Organocatalytic Asymmetric Condensation DOI

Fengrui Che,

Junyuan Hu,

Minghong Liao

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 26, 2024

Enantioenriched phosphorus(V)-stereogenic compounds, featuring a pentavalent phosphorus atom as the stereogenic center, are crucial in various natural products, drugs, bioactive molecules, and catalysts/ligands. While handful of stereoselective synthetic approaches have been developed, achieving direct stereocontrol at through catalytic generation phosphorus(V)-heteroatom bonds continues to be formidable challenge. Here, we disclose an organocatalytic asymmetric condensation strategy that employs novel activation mode stable feedstock phosphinic acids by formation mixed anhydride reactive species facilitate further catalyst-controlled P-O bond formations, involving dynamic kinetic transformation (DYKAT) process with alcohol nucleophiles via cinchonidine-derived bifunctional catalyst. The resulting H-phosphinate intermediates allow stereospecific derivatizations, affording modular access diverse library chiral phosphonates phosphonamidates notable antibacterial activity. Furthermore, this platform facilitates P-O/N coupling products presenting valuable tool for medicine agrochemical discovery.

Language: Английский

Citations

Stereogenic P(V) Synthesis via Catalytic Continuous Substitutions DOI

Gaoliang Zheng,

Yuchen Zhang, Jingming Zhang

et al.

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

Published: April 9, 2025

Phosphorus(V) stereocenters that are fully substituted by heteroatoms play important roles in bioactive molecules and organocatalysts. Existing methods to achieve such motifs rely almost entirely on resolution or diastereocontrol, prefunctionalized substrates usually required generate specific P(V) stereocenters. In contrast, related catalytic rare, no generally applicable method is described. Here, we report a modular strategy access broad variety of stereogenic-at-phosphorus skeletons, including ProTide analogs, alkoxylphosphoramidates, phosphates, phosphorothioates, phosphonamidates, through designed enantioselective continuous substitutions simple precursors. The nucleophilic substitution sequence readily determined the stereoconfiguration products. Concise synthesis analogs drug demonstrated practical value protocol. Experimental computational studies unveiled unique π-π stacking effect chalcogen bonding interaction between catalyst substrate as origin stereoselectivity.

Language: Английский

Citations

Synthesis and crystal structure of methylphosphonic dichloride and N,N-diethyl-P-methylphosphonamidic chloride DOI

Almaz A. Zagidullin,

Farida F. Naileva,

Robert R. Fayzullin

et al.

Journal of Molecular Structure, Journal Year: 2025, Volume and Issue: unknown, P. 142323 - 142323

Published: April 1, 2025

Language: Английский

Citations

Enantio- and Diastereoselective Synthesis of P-Stereogenic Phospholane Oxides via Cobalt-Catalyzed Hydroalkylation DOI

Dao‐Yong Zhu, Yating Zhang,

Fu Cheng

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 10, 2025

Chiral phospholane ligands and catalysts have been widely applied in asymmetric catalysis synthesis. However, the construction of chiral skeleton remains challenging primarily relies on use auxiliaries or resolution. In this work, a highly enantioselective diastereoselective synthesis P-stereogenic oxides has achieved through cobalt-catalyzed desymmetric hydroalkylation strategy. This method enables two discrete stereocenters with excellent yields enantiomeric excesses.

Language: Английский

Citations

NHC-catalyzed covalent activation and control of P(V)-stereogenic phosphorus centers via phosphonyl azolium intermediates DOI

Yanyan Wang,

Kuohong Chen,

Fengrui Che

et al.

Chem, Journal Year: 2025, Volume and Issue: unknown, P. 102586 - 102586

Published: May 1, 2025

Language: Английский

Citations

Poison to promise: The resurgence of organophosphorus fluoride chemistry DOI

William P. Chappell,

Natalie Schur,

James A. Vogel

et al.

Chem, Journal Year: 2024, Volume and Issue: 10(6), P. 1644 - 1654

Published: May 9, 2024

Language: Английский

Citations

Enantioselective Desymmetrization of Phosphinic Acids via Cu-Catalyzed O-Arylation DOI

Ming Yan, Jiawei Zou, Dongmei Fang

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4719 - 4725

Published: March 6, 2025

Language: Английский

Citations