-
ACS Central Science Apr 2021Phosphorus-based organocatalysis encompasses several subfields that have undergone rapid growth in recent years. This Outlook gives an overview of its various aspects.... (Review)
Review
Phosphorus-based organocatalysis encompasses several subfields that have undergone rapid growth in recent years. This Outlook gives an overview of its various aspects. In particular, we highlight key advances in three topics: nucleophilic phosphine catalysis, organophosphorus catalysis to bypass phosphine oxide waste, and organophosphorus compound-mediated single electron transfer processes. We briefly summarize five additional topics: chiral phosphoric acid catalysis, phosphine oxide Lewis base catalysis, iminophosphorane super base catalysis, phosphonium salt phase transfer catalysis, and frustrated Lewis pair catalysis. Although it is not catalytic in nature, we also discuss novel discoveries that are emerging in phosphorus(V) ligand coupling. We conclude with some ideas about the future of organophosphorus catalysis.
PubMed: 34056085
DOI: 10.1021/acscentsci.0c01493 -
International Journal of Molecular... Aug 2021Polybetaines, that have moieties bearing both cationic (quaternary ammonium group) and anionic groups (carboxylate, sulfonate, phosphate/phosphinate/phosphonate groups)... (Review)
Review
Polybetaines, that have moieties bearing both cationic (quaternary ammonium group) and anionic groups (carboxylate, sulfonate, phosphate/phosphinate/phosphonate groups) situated in the same structural unit represent an important class of smart polymers with unique and specific properties, belonging to the family of zwitterionic materials. According to the anionic groups, polybetaines can be divided into three major classes: poly(carboxybetaines), poly(sulfobetaines) and poly(phosphobetaines). The structural diversity of polybetaines and their special properties such as, antifouling, antimicrobial, strong hydration properties and good biocompatibility lead to their use in nanotechnology, biological and medical fields, water remediation, hydrometallurgy and the oil industry. In this review we aimed to highlight the recent developments achieved in the field of biomedical applications of polybetaines such as: antifouling, antimicrobial and implant coatings, wound healing and drug delivery systems.
Topics: Animals; Anti-Infective Agents; Betaine; Drug Delivery Systems; Humans; Wound Healing
PubMed: 34502230
DOI: 10.3390/ijms22179321 -
Chemistry (Weinheim An Der Bergstrasse,... Oct 2021The reaction of the intramolecular germylene-phosphine Lewis pair (o-PPh )C H GeAr* (1) with Group 15 element trichlorides ECl (E=P, As, Sb) was investigated. After...
The reaction of the intramolecular germylene-phosphine Lewis pair (o-PPh )C H GeAr* (1) with Group 15 element trichlorides ECl (E=P, As, Sb) was investigated. After oxidative addition, the resulting compounds (o-PPh )C H (Ar*)Ge(Cl)ECl (2: E=P, 3: E=As, 4: E=Sb) were reduced by using sodium metal or LiHBEt . The molecular structures of the phosphine-stabilized phosphinidene (o-PPh )C H (Ar*)Ge(Cl)P (5), arsinidene (o-PPh )C H (Ar*)Ge(Cl)As (6) and stibinidene (o-PPh )C H (Ar*)Ge(Cl)Sb (7) are presented; they feature a two-coordinate low-valent Group 15 element. After chloride abstraction, a cyclic germaphosphene [(o-PPh )C H (Ar*)GeP] [B(C H (CF ) ) ] (8) was isolated. The P NMR data of the germaphosphene were compared with literature examples and analyzed by quantum chemical calculations. The phosphinidene was treated with [iBu AlH] , and the product of an Al-H addition to the low-valent phosphorus atom (o-PPh )C H (Ar*)Ge(H)P(H)Al(C H ) (9) was characterized.
PubMed: 34291518
DOI: 10.1002/chem.202102320 -
Bioorganic & Medicinal Chemistry Dec 2023Clinically manifested resistance of bacteria to antibiotics has emerged as a global threat to society and there is an urgent need for the development of novel classes of... (Review)
Review
Clinically manifested resistance of bacteria to antibiotics has emerged as a global threat to society and there is an urgent need for the development of novel classes of antibacterial agents. Recently, the use of phosphorus in antibacterial agents has been explored in quite an unprecedent manner. In this comprehensive review, we summarize the use of phosphorus-containing moieties (phosphonates, phosphonamidates, phosphonopeptides, phosphates, phosphoramidates, phosphinates, phosphine oxides, and phosphoniums) in compounds with antibacterial effect, including their use as β-lactamase inhibitors and antibacterial disinfectants. We show that phosphorus-containing moieties can serve as novel pharmacophores, bioisosteres, and prodrugs to modify pharmacodynamic and pharmacokinetic properties. We further discuss the mechanisms of action, biological activities, clinical use and highlight possible future prospects.
Topics: Phosphorus; Anti-Bacterial Agents; beta-Lactamase Inhibitors; Bacteria; Organophosphonates
PubMed: 37939493
DOI: 10.1016/j.bmc.2023.117512 -
Chemical Reviews Jun 2021Bioorthogonal phosphines were introduced in the context of the Staudinger ligation over 20 years ago. Since that time, phosphine probes have been used in myriad... (Review)
Review
Bioorthogonal phosphines were introduced in the context of the Staudinger ligation over 20 years ago. Since that time, phosphine probes have been used in myriad applications to tag azide-functionalized biomolecules. The Staudinger ligation also paved the way for the development of other phosphorus-based chemistries, many of which are widely employed in biological experiments. Several reviews have highlighted early achievements in the design and application of bioorthogonal phosphines. This review summarizes more recent advances in the field. We discuss innovations in classic Staudinger-like transformations that have enabled new biological pursuits. We also highlight relative newcomers to the bioorthogonal stage, including the cyclopropenone-phosphine ligation and the phospha-Michael reaction. The review concludes with chemoselective reactions involving phosphite and phosphonite ligations. For each transformation, we describe the overall mechanism and scope. We also showcase efforts to fine-tune the reagents for specific functions. We further describe recent applications of the chemistries in biological settings. Collectively, these examples underscore the versatility and breadth of bioorthogonal phosphine reagents.
Topics: Azides; Benzene Derivatives; Cycloaddition Reaction; Phosphines
PubMed: 34101453
DOI: 10.1021/acs.chemrev.1c00014 -
Current Issues in Molecular Biology Mar 2023Phosphine is the most widely used fumigant for stored grains due to a lack of better alternatives, all of which have serious shortcomings that restrict their use. The... (Review)
Review
Phosphine is the most widely used fumigant for stored grains due to a lack of better alternatives, all of which have serious shortcomings that restrict their use. The extensive use of phosphine has led to the development of resistance among insect pests of grain, which threatens its status as a reliable fumigant. Understanding the mode of action of phosphine as well as its resistance mechanisms provides insight that may lead to improved phosphine efficacy and pest control strategies. The mechanisms of action in phosphine vary from disrupting metabolism and oxidative stress to neurotoxicity. Phosphine resistance is genetically inherited and is mediated by the mitochondrial dihydrolipoamide dehydrogenase complex. In this regard, laboratory studies have revealed treatments that synergistically enhance phosphine toxicity that may be used to suppress resistance development and enhance efficacy. Here, we discuss the reported phosphine modes of action, mechanisms of resistance and interactions with other treatments.
PubMed: 36975531
DOI: 10.3390/cimb45030161 -
Beilstein Journal of Organic Chemistry 2023Photoredox catalysis plays a crucial role in contemporary synthetic organic chemistry. Since the groundbreaking work of Shang and Fu on photocatalytic decarboxylative... (Review)
Review
Photoredox catalysis plays a crucial role in contemporary synthetic organic chemistry. Since the groundbreaking work of Shang and Fu on photocatalytic decarboxylative alkylations in 2019, a wide range of organic transformations, such as alkylation, alkenylation, cyclization, amination, iodination, and monofluoromethylation, have been progressively achieved using a combination of iodide and PPh. In this review, we primarily focus on summarizing the recent advancements in inexpensive and readily available iodide/phosphine-mediated photoredox radical transformations.
PubMed: 38033449
DOI: 10.3762/bjoc.19.131 -
ChemistryOpen Aug 2020Bioorthogonal reactions including the bioorthogonal ligations and cleavages have become an active field of research in chemical biology, and they play important roles in... (Review)
Review
Bioorthogonal reactions including the bioorthogonal ligations and cleavages have become an active field of research in chemical biology, and they play important roles in chemical modification and functional regulation of biomolecules. This review summarizes the developments and applications of the representative bioorthogonal reactions including the Staudinger reactions, the metal-mediated bioorthogonal reactions, the strain-promoted cycloadditions, the inverse electron demand Diels-Alder reactions, the light-triggered bioorthogonal reactions, and the reactions of chloroquinoxalines and -dithiophenols.
Topics: Alkynes; Azides; Catalysis; Cycloaddition Reaction; Heterocyclic Compounds, 1-Ring; Light; Metals, Heavy; Phosphines; Photolysis; Quinoxalines; Sulfhydryl Compounds
PubMed: 32817809
DOI: 10.1002/open.202000128 -
Medicine in Drug Discovery Dec 2020Phosphorus-containing drugs belong to an important class of therapeutic agents and are widely applied in daily clinical practices. Structurally, the... (Review)
Review
Phosphorus-containing drugs belong to an important class of therapeutic agents and are widely applied in daily clinical practices. Structurally, the phosphorus-containing drugs can be classified into phosphotriesters, phosphonates, phosphinates, phosphine oxides, phosphoric amides, bisphosphonates, phosphoric anhydrides, and others; functionally, they are often designed as prodrugs with improved selectivity and bioavailability, reduced side effects and toxicity, or biomolecule analogues with endogenous materials and antagonistic endoenzyme supplements. This review summarized the phosphorus-containing drugs currently on the market as well as a few promising molecules at clinical studies, with particular emphasis on their structural features, biological mechanism, and indications.
PubMed: 32864606
DOI: 10.1016/j.medidd.2020.100063 -
Frontiers in Chemistry 2023Despite the promising pharmacological activity and material properties of five-membered heterocyclic compounds containing phosphorus and nitrogen, synthetic examples of...
Despite the promising pharmacological activity and material properties of five-membered heterocyclic compounds containing phosphorus and nitrogen, synthetic examples of them have been rather limited due to the instability of phosphorus toward air and water. In this study, 1,3-benzoazaphosphol analogues were selected as target molecules, and various synthetic routes were examined to establish a fundamental technology for the introduction of phosphorus groups into aromatic rings and formation of five-membered rings containing phosphorus and nitrogen by cyclization. As a result, we found that 2-aminophenyl(phenyl)phosphine is an extremely promising synthetic intermediate with high stability and easy handling. Furthermore, 2-methyl-3-phenyl-2,3-dihydro-1-benzo[][1,3]azaphosphole and 3-phenyl-2,3-dihydro-1-benzo[][1,3]azaphosphole-2-thione as synthetically useful 1,3-benzoazaphosphol analogues were successfully synthesized by using 2-aminophenyl(phenyl)phosphine as a key intermediate.
PubMed: 37304686
DOI: 10.3389/fchem.2023.1174895