Recent advances in radical phosphorylation DOI Open Access

Yuan Niu,

Shang‐Dong Yang

Chemical Synthesis, Journal Year: 2021, Volume and Issue: unknown

Published: Jan. 1, 2021

Chemical Synthesis is an open access peer-reviewed journal publishing original research involving all areas of the chemical sciences. The aims to be premier resource seminal and insightful showcases for researchers in both academia industry, providing a platform inspiration future chemistry. intends serve as preeminent international chemistry has ambition among first choices chemists publication their discoveries.

Language: Английский

Development of a General Organophosphorus Radical Trap: Deoxyphosphonylation of Alcohols DOI
Noah B. Bissonnette, Niels Bisballe, Andrew V. Tran

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(12), P. 7942 - 7949

Published: March 12, 2024

Here we report the design of a general, redox-switchable organophosphorus alkyl radical trap that enables synthesis broad range C(sp3)–P(V) modalities. This "plug-and-play" approach relies upon in situ activation alcohols and O═P(R2)H motifs, two broadly available inexpensive sources molecular complexity. The mild, photocatalytic deoxygenative strategy described herein allows for direct conversion sugars, nucleosides, complex pharmaceutical architectures to their analogs. includes facile incorporation medicinally relevant phosphonate ester prodrugs.

Language: Английский

Citations

22
Direct Deaminative Functionalization DOI
Balu D. Dherange, Mingbin Yuan, Christopher B. Kelly

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 145(1), P. 17 - 24

Published: Dec. 22, 2022

Selective functional group interconversions in complex molecular settings underpin many of the challenges facing modern organic synthesis. Currently, a privileged subset groups dominates this landscape, while others, despite their abundance, are sorely underdeveloped. Amines epitomize dichotomy; they abundant but otherwise intransigent toward direct interconversion. Here, we report an approach that enables conversion amines to bromides, chlorides, iodides, phosphates, thioethers, and alcohols, heart which is deaminative carbon-centered radical formation process using anomeric amide reagent. Experimental computational mechanistic studies demonstrate successful functionalization relies not only on outcompeting H-atom transfer incipient also generation polarity-matched, productive chain-carrying radicals continue react efficiently. The overall implications technology for interconverting amine libraries were evaluated via high-throughput parallel synthesis applied development one-pot diversification protocols.

Language: Английский

Citations

52
Phosphonylation of alkyl radicals DOI Creative Commons

Junyue Yin,

Xinru Lin,

Linxiang Chai

et al.

Chem, Journal Year: 2023, Volume and Issue: 9(7), P. 1945 - 1954

Published: April 12, 2023

Language: Английский

Citations

35
Convergent Deboronative and Decarboxylative Phosphonylation Enabled by the Phosphite Radical Trap “BecaP” DOI Creative Commons
Santosh K. Pagire, Chao Shu,

Dominik Reich

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(33), P. 18649 - 18657

Published: Aug. 8, 2023

Carbon-phosphorus bond formation is significant in synthetic chemistry because phosphorus-containing compounds offer numerous indispensable biochemical roles. While there a plethora of methods to access organophosphorus compounds, phosphonylations readily accessible alkyl radicals form aliphatic phosphonates are rare and not commonly used synthesis. Herein, we introduce novel phosphorus radical trap "BecaP" that enables facile efficient phosphonylation under visible light photocatalytic conditions. Importantly, the ambiphilic nature BecaP allows redox neutral reactions with both nucleophilic (activated by single-electron oxidation) electrophilic reduction) precursors. Thus, broad scope feedstock potassium trifluoroborate salts active carboxylate esters could be employed, each class substrate proceeding through distinct mechanistic pathway. The mild conditions applicable late-stage installation phosphonate motifs into medicinal agents natural products, which showcased straightforward conversion baclofen (muscle relaxant) phaclofen (GABAB antagonist).

Language: Английский

Citations

29
Photocatalytic Hydrogen Atom Transfer-Induced Arbuzov-Type α-C(sp3)–H Phosphonylation of Aliphatic Amines DOI Open Access
Zhexuan Lei, Weigang Zhang, Jie Wu

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(24), P. 16105 - 16113

Published: Dec. 5, 2023

Despite remarkable progress in photocatalytic hydrogen atom transfer (HAT)-induced C(sp3)–H functionalization, achieving to C(sp3)–P transformation by the HAT process remains highly challenging due P-reagents' compatibility issues. α-Aminophosphonic acids have shown great potential medicinal chemistry, yet their synthesis is hindered limited substrate scopes, poor functional group tolerance, and reliance on prefunctionalized substrates, restricting broad applications. Herein, we report HAT-induced α-C(sp3)–H phosphonylation of aliphatic amines, providing rapid access structurally diverse α-aminophosphonates from abundant amines. Leveraging intramolecular HAT, radical polar crossover, an Arbuzov-type cascade, challenges associated with were overcome. This protocol features base-free, redox-neutral, mild conditions employing amines as limiting reagents, allows for late-stage complex drug molecules possessing amine moieties.

Language: Английский

Citations

26
Synthetic Methods for Azaheterocyclic Phosphonates and Their Biological Activity: An Update 2004–2024 DOI
Martha C. Mayorquín‐Torres, Andreas Simoens, Eli Bonneure

et al.

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(12), P. 7907 - 7975

Published: May 29, 2024

The increasing importance of azaheterocyclic phosphonates in the agrochemical, synthetic, and medicinal field has provoked an intense search development synthetic routes for obtaining novel members this family compounds. This updated review covers methodologies established since 2004, focusing on synthesis phosphonates, which phosphonate moiety is directly substituted onto to structure. Emphasizing recent advances, classifies newly developed approaches according ring size providing information biological activities whenever available. Furthermore, summarizes various methods formation C–P bonds, examining sustainable such as Michaelis–Arbuzov reaction, Michaelis–Becker Pudovik Hirao coupling, Kabachnik–Fields reaction. After analyzing applications investigated years, a predominant focus evaluation these compounds anticancer agents evident. emerging underline versatility potential compounds, highlighting need continued research expand interesting family.

Language: Английский

Citations

14
Recent progress on the functionalization of white phosphorus in China DOI Creative Commons
Xinlei Huangfu, Zhongzhen Wang, Yu Chen

et al.

National Science Review, Journal Year: 2024, Volume and Issue: 11(6)

Published: May 2, 2024

Direct synthesis of organophosphorus compounds from white phosphorus represents a significant but challenging subject, especially in the context ongoing efforts to comprehensively improve phosphorus-derived chemical industry driven by sustainability and safety concerns. China is world's largest producer phosphorus, creating demand for green transformation this crucial feedstock. This review provides an overview advancements activation Chinese research teams, focusing on direct construction P‒C/N/O/S/M bonds phosphorus. Additionally, we offer some insights into prospective directions future. paper aims attract more researchers engage area, stimulating follow-up exploration fostering enduring advances.

Language: Английский

Citations

10
N-Protonated Acridinium Catalyst Enables Anti-Markovnikov Hydration of Unconjugated Tri- and Disubstituted Olefins DOI Creative Commons

Boris A. van der Worp,

Tobias Ritter

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: 147(6), P. 4736 - 4742

Published: Jan. 31, 2025

The preparation of alcohols with anti-Markovnikov selectivity directly from olefins and water is a sought-after reaction due to its atom-economy potential cost-effectiveness. Herein, we present the first general method for direct, catalytic hydration unconjugated tri- disubstituted olefins. key advancement made possible by an oxidative (E*red = 2.15 V) N-H acridinium catalyst, which allowed functionalization alkenes that were previously unreactive in such transformations their high oxidation potential. developed protocol not limited but also enables other hydrofunctionalizations, as hydroetherifications, following same mechanistic pathway.

Language: Английский

Citations

1
Recent Advances in Theoretical Studies on Cu-Mediated Bond Formation Mechanisms Involving Radicals DOI
Ji‐Ren Liu,

Guo-Xiong Xu,

Li‐Gao Liu

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(4), P. 2429 - 2454

Published: Feb. 1, 2024

Copper-catalyzed radical transformations establish a powerful toolkit to construct versatile complex organic compounds. The copper-mediated bond formation step of radicals plays critical role in controlling chemo- and stereoselectivity copper-catalyzed transformation reactions. This involves three possible pathways: ion-type formation, substitution, reductive elimination. review highlights the recent advances theoretical studies on mechanisms models selectivity Cu-mediated radical-involved providing general mechanistic comprehension this key elementary copper catalysis.

Language: Английский

Citations

7
Recent advances in electrochemical C—H phosphorylation DOI Creative Commons
Yulia H. Budnikova,

Egor L. Dolengovsky,

Maxim V. Tarasov

et al.

Frontiers in Chemistry, Journal Year: 2022, Volume and Issue: 10

Published: Nov. 3, 2022

The activation of C–H bond, and its direct one-step functionalization, is one the key synthetic methodologies that provides access to a variety practically significant compounds. Particular attention focused on modifications obtained at final stages synthesis complicated molecules, which requires high tolerance presence existing functional groups. Phosphorus an indispensable element life, phosphorus chemistry now experiencing renaissance due new emerging applications in medicinal chemistry, materials (polymers, flame retardants, organic electronics, photonics), agricultural (herbicides, insecticides), catalysis (ligands) other important areas science technology. In this regard, search for new, more selective, low-waste routes become relevant. context, electrosynthesis has proven be eco-efficient convenient approach many respects, where reagents are replaced by electrodes, reactants applied potential determines their “oxidizing or reducing ability”. An electrochemical such processes being developed rapidly demonstrates some advantages over traditional classical methods C-H phosphorylation. main reasons success exclusion excess from reaction system: as oxidants, agents, sometimes metal and/or improvers, challenge isolation, increase wastes reduce yield frequent incompatibility with these Ideal conditions include electron reactant (regulated potential) by-products hydrogen hydrocarbon. review summarizes analyzes achievements preparation various derivatives carbon-phosphorus bonds, collects data redox properties most commonly used precursors. Electrochemically induced reactions both without catalyst metals, competitive oxidation precursors leads either bond generation phosphorus-centered radicals (radical cations) states will examined. focuses publications past 5 years.

Language: Английский

Citations

28