Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2017 - 2291

Published: Nov. 23, 2021

We present here a review of the photochemical and electrochemical applications multi-site proton-coupled electron transfer (MS-PCET) in organic synthesis. MS-PCETs are redox mechanisms which both an proton exchanged together, often concerted elementary step. As such, MS-PCET can function as non-classical mechanism for homolytic bond activation, providing opportunities to generate synthetically useful free radical intermediates directly from wide variety common functional groups. introduction practitioner’s guide reaction design, with emphasis on unique energetic selectivity features that characteristic this class. then chapters oxidative N–H, O–H, S–H, C–H homolysis methods, generation corresponding neutral species. Then, reductive PCET activations involving carbonyl, imine, other X═Y π-systems, heteroarenes, where ketyl, α-amino, heteroarene-derived radicals be generated. Finally, we asymmetric catalysis materials device applications. Within each chapter, subdivide by group undergoing homolysis, thereafter type transformation being promoted. Methods published prior end December 2020 presented.

Language: Английский

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Recent Advances in the Construction of Phosphorus‐Substituted Heterocycles, 2009–2019

Advanced Synthesis & Catalysis, Journal Year: 2020, Volume and Issue: 362(9), P. 1724 - 1818

Published: Jan. 20, 2020

Abstract Phosphorus‐substituted heterocycles represent an important class of organophosphorus compounds, which not only widely exist in biologically active pharmaceuticals, agrochemicals, but also have widespread applications material science and organic synthesis as ligands for transition metal complexes. The such compounds integrates the development new synthetic methods exploration efficient catalytic systems, reflects latest achievements organic, metal, photo even electrochemical catalysis, facilitates sufficient quantities related potential medicinal agents biological probes this area. Over past few decades, two major strategies been established toward phosphorus‐substituted heterocycles. This review summarizes recent progress field discusses reaction mechanisms detail. advantages limitations each subdivisional tactic are presented, opportunities still open outlined. magnified image

Language: Английский

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Enantiodivergent Kinetic Resolution of 1,1′‐Biaryl‐2,2′‐Diols and Amino Alcohols by Dipeptide‐Phosphonium Salt Catalysis Inspired by the Atherton–Todd Reaction

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(27), P. 14921 - 14930

Published: March 17, 2021

Abstract A highly enantiodivergent organocatalytic method is disclosed for the synthesis of atropisomeric biaryls via kinetic resolution inspired by a dipeptide‐phosphonium salt‐catalyzed Atherton–Todd (A‐T) reaction. This flexible approach led to both R ‐ and S ‐enantiomers fine‐tuning bifunctional phosphonium with excellent selectivity factors ( s ) up 1057 525, respectively. The potential newly synthesized O‐phosphorylated biaryl diols was illustrated axially chiral organophosphorus compounds. Mechanistic investigations suggest that halide catalyst differentiates between in‐situ‐generated P‐species in A‐T process, mainly involving phosphoryl chloride phosphoric anhydride, thus leading O‐phosphorylation reactions. Furthermore hydrogen bonding interactions catalysts phosphorus molecules were crucial asymmetric induction.

Language: Английский

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Visible-light-driven multicomponent reactions to access S-alkyl phosphorothioates using elemental sulfur as the sulfur source

Green Chemistry, Journal Year: 2022, Volume and Issue: 24(12), P. 4915 - 4920

Published: Jan. 1, 2022

A convenient and eco-friendly visible-light promoted multicomponent protocol has been developed for the synthesis of S -alkyl phosphorothioates by using elemental sulfur as cheap odorless source.

Language: Английский

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A phosphoryl radical-initiated Atherton–Todd-type reaction under open air

Chemical Communications, Journal Year: 2019, Volume and Issue: 56(9), P. 1357 - 1360

Published: Dec. 20, 2019

A phosphoryl radical-initiated Atherton–Todd-type reaction enables the phosphorylation of alcohols, phenols, and amines under mild conditions.

Language: Английский

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Tf₂O/DMSO-Promoted P–O and P–S Bond Formation: A Scalable Synthesis of Multifarious Organophosphinates and Thiophosphates

Organic Letters, Journal Year: 2021, Volume and Issue: 23(5), P. 1541 - 1547

Published: Feb. 24, 2021

A Tf2O/DMSO-based system for the dehydrogenative coupling of a wide range alcohols, phenols, thiols, and thiophenols with diverse phosphorus reagents has been developed. This metal- strong-oxidant-free strategy provides facile approach to great variety organophosphinates thiophosphates. The simple reaction system, good functional-group tolerance, broad substrate scope enable application this method modification natural products direct synthesis bioactive molecules flame retardants.

Language: Английский

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TsCl promoted deoxygenative phosphorothiolation of quinoline N-oxides towards S-quinolyl phosphorothioates

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(12), P. 2409 - 2413

Published: Jan. 1, 2024

A convenient, efficient and practical approach for the synthesis of

Language: Английский

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Electrochemical oxidative thiocyanation and amination of enaminones towards the synthesis of multi-substituted alkenes

Green Chemistry, Journal Year: 2020, Volume and Issue: 23(2), P. 763 - 766

Published: Dec. 11, 2020

A highly stereoselective synthesis of thiocyanated enaminones was achieved by an electrochemical process, which involved C–H bond thiocyanation and vinyl C–N transamination.

Language: Английский

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Electrochemical Phosphorylation of Organic Molecules

The Chemical Record, Journal Year: 2020, Volume and Issue: 20(12), P. 1530 - 1552

Published: Oct. 5, 2020

Abstract Organophosphorus chemistry is a broad field with multi‐dimensional applications in research area of organic, biology, drug design and agrochemicals. Conventional methods have been adopted extensively to access phosphorylated compounds that rely on the use toxic, moisture sensitive phosphorylating agents occur presence oxidants, catalysts, as well high temperatures harsh conditions are required for complete transformations. However, recent progress has made phosphorylation reactions using electricity introduce green sustainable synthetic procedures. These can be performed at mild proceed excellent atom economy. Herein, we targeted electrochemical generation new bonds such C(sp 3 ) −P, 2 O−P, N−P, S−P Se−P. This review aimed offer an overview developments methodology easy organophosphorus electrochemistry.

Language: Английский

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Electrochemical Oxidative Dehydrogenative Phosphorylation of N-Heterocycles with P(O)–H Compounds in Imidazolium-Based Ionic Liquid

Organic Letters, Journal Year: 2020, Volume and Issue: 22(8), P. 3062 - 3066

Published: April 7, 2020

We report a direct and green electrochemical oxidative cross-dehydrogenative coupling reaction of N-heterocycles with hydrogen phosphoryl compounds under external oxidant-free conditions. Various phosphorylation products substituted carbazoles indoles are assembled in modest to excellent yields. A release process is preliminarily demonstrated H2 the sole byproduct. An imidazolium based ionic liquid selected as optimal electrolyte.

Language: Английский

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