Efficient and Sustainable Electrosynthesis of N-Sulfonyl Iminophosphoranes by the Dehydrogenative P–N Coupling Reaction DOI Creative Commons

Jessica C. Bieniek,

Darryl Nater,

Sara L. Eberwein

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(6), P. 2188 - 2196

Published: April 18, 2024

Iminophosphoranes are commonly used reagents in organic synthesis and are, therefore, of great interest. An efficient sustainable iodide-mediated electrochemical N-sulfonyl iminophosphoranes from readily available phosphines sulfonamides is reported. This method features low amounts supporting electrolytes, inexpensive electrode materials, a simple galvanostatic setup, high conversion rates. The broad applicability could be demonstrated by synthesizing 20 examples yields up to 90%, having diverse functional groups including chiral moieties biologically relevant species. Furthermore, electrolysis was performed on g scale run repetitive mode recycling the electrolyte, which illustrates suitability for large-scale production. A reaction mechanism involving mediation iodide-based electrolyte proposed, completely agreeing with all results.

Language: Английский

Scalable Flow Electrosynthesis of Iminophosphoranes DOI
Dan Lehnherr, Longrui Chen, François Lévesque

et al.

Organic Process Research & Development, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 7, 2025

A scalable electrochemical process to synthesize iminophosphorane ligands is reported. The application of these iminophosphoranes was recently reported in Ni-catalyzed cross-electrophile and C–N cross-couplings. use parallel plate flow reactors enables the synthesis on a multigram scale, with selected examples up 0.6 kg scale. Direct crystallization from end reaction mixture for provides facile isolation processes. This article also details improvements our capabilities across scales, including addressing material compatibility issues, increasing accessible range rates, integration analytical technology tools.

Language: Английский

Citations

2
Adoption of Electrochemistry within the Pharmaceutical Industry: Insights from an Industry-Wide Survey DOI
Antonio C. Ferretti, Benjamin Cohen, Lin Deng

et al.

Organic Process Research & Development, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 27, 2025

Language: Английский

Citations

2
Synthesis, Characterization, and Catalytic Activity of Ni(0) (DQ)dtbbpy, an Air-Stable, Bifunctional Red-Light-Sensitive Precatalyst DOI
Jingsheng Li, Pengpeng Wang, Bing Bai

et al.

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

Published: Feb. 5, 2025

Despite a well-established and growing body of work on nickel(0) precatalysts, the potential complexes as bifunctional precatalysts remains underexplored. In this study, we synthesized, characterized, evaluated catalytic activity (Ni(0)(DQ)dtbbpy), bifunctional, red-light-sensitive, air-stable complex. Owing to its unique photophysical properties, it effectively catalyzed etherification amination aryl bromides under 620–630 nm light irradiation, functioning both photocatalyst an active metal catalyst. Mechanistic studies density functional theory (DFT) calculations further confirmed exceptional absorption properties Ni(0)(DQ)dtbbpy in red-light region, well electron transfer process triggered by irradiation.

Language: Английский

Citations

1
A Scalable Flow Electrolysis of Heterogeneous Mixtures Using a Rotating Cylinder Electrode Reactor: Access to a Chiral Iminophosphorane DOI

Felix Xu,

Longrui Chen, Dan Lehnherr

et al.

Organic Process Research & Development, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 27, 2025

We report the application of rotating cylinder electrode (RCE) reactors for electrolysis heterogeneous reactions in batch and recirculating flow. A scalable method synthesis an N-cyano iminophosphorane ligand RCE reactor is also reported. In development this process, a graphite felt attached to inner impervious was used as anode, outer stainless steel wall cathode. The reaction first evaluated using small optimize spinning rate, supporting electrolyte, current density. optimal condition then scaled up medium-sized with modifications adapt it flow process. electrosynthesis demonstrated 100 g scale, impact temperature investigated. Finally, operationally simple direct crystallization water antisolvent provided chiral 74% isolated yield on scale from commercially available (S)-BINAP bis(trimethylsilyl)carbodiimide.

Language: Английский

Citations

0
Trendbericht: Organische Chemie 2025 DOI Open Access
Martin Breugst, Jennifer N. Andexer,

Lena Barra

et al.

Nachrichten aus der Chemie, Journal Year: 2025, Volume and Issue: 73(3), P. 40 - 70

Published: Feb. 28, 2025

Abstract Highlights von November 2023 bis 2024: die erste Einelektron‐C–C‐σ‐Bindung und Anti‐Bredt‐Verbindung; gesättigte Heterocyclen elektrochemisch funktionalisieren; Ausrichten diskotischer Flüssigkristalle; enantioselektive Wagner‐Meerwein‐Umlagerung reiner Aliphaten; photokatalytisch Furanen zu Pyrrolen; mit Ammoniak primären Arylaminen; Metallschrott recyceln ionischen Flüssigkeiten; terminale Alkene Ni‐Katalysatoren zum (Z)‐ oder (E)‐Alken isomerisieren;neue Fungizide, Medikamente Alkaloide.

Citations

0
Recent advances in the electrochemical synthesis of organophosphorus compounds DOI Creative Commons
Babak Kaboudin, Milad Behroozi,

Sepideh Sadighi

et al.

Beilstein Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 21, P. 770 - 797

Published: April 16, 2025

In this review, we describe recent advances in electrochemical green methods for the synthesis of various organophosphorus compounds through formation phosphorus–carbon, phosphorus–nitrogen, phosphorus–oxygen, phosphorus–sulfur, and phosphorus–selenium bonds. The impact different electrodes is also discussed matter. Graphite, platinum, RVC, nickel have been used extensively compounds. made method a promising preparing structures. This review an introduction to encourage scientists use electrosynthesis as green, precise, low-cost prepare phosphorous

Language: Английский

Citations

0
Efficient and Sustainable Electrosynthesis of N-Sulfonyl Iminophosphoranes by the Dehydrogenative P–N Coupling Reaction DOI Creative Commons

Jessica C. Bieniek,

Darryl Nater,

Sara L. Eberwein

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(6), P. 2188 - 2196

Published: April 18, 2024

Iminophosphoranes are commonly used reagents in organic synthesis and are, therefore, of great interest. An efficient sustainable iodide-mediated electrochemical N-sulfonyl iminophosphoranes from readily available phosphines sulfonamides is reported. This method features low amounts supporting electrolytes, inexpensive electrode materials, a simple galvanostatic setup, high conversion rates. The broad applicability could be demonstrated by synthesizing 20 examples yields up to 90%, having diverse functional groups including chiral moieties biologically relevant species. Furthermore, electrolysis was performed on g scale run repetitive mode recycling the electrolyte, which illustrates suitability for large-scale production. A reaction mechanism involving mediation iodide-based electrolyte proposed, completely agreeing with all results.

Language: Английский

Citations

2