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Chemical Reviews Oct 2018The hallmark of nucleophilic phosphine catalysis is the initial nucleophilic addition of a phosphine to an electrophilic starting material, producing a reactive... (Review)
Review
The hallmark of nucleophilic phosphine catalysis is the initial nucleophilic addition of a phosphine to an electrophilic starting material, producing a reactive zwitterionic intermediate, generally under mild conditions. In this Review, we classify nucleophilic phosphine catalysis reactions in terms of their electrophilic components. In the majority of cases, these electrophiles possess carbon-carbon multiple bonds: alkenes (section 2), allenes (section 3), alkynes (section 4), and Morita-Baylis-Hillman (MBH) alcohol derivatives (MBHADs; section 5). Within each of these sections, the reactions are compiled based on the nature of the second starting material-nucleophiles, dinucleophiles, electrophiles, and electrophile-nucleophiles. Nucleophilic phosphine catalysis reactions that occur via the initial addition to starting materials that do not possess carbon-carbon multiple bonds are collated in section 6. Although not catalytic in the phosphine, the formation of ylides through the nucleophilic addition of phosphines to carbon-carbon multiple bond-containing compounds is intimately related to the catalysis and is discussed in section 7. Finally, section 8 compiles miscellaneous topics, including annulations of the Hüisgen zwitterion, phosphine-mediated reductions, iminophosphorane organocatalysis, and catalytic variants of classical phosphine oxide-generating reactions.
Topics: Alcohols; Alkenes; Alkynes; Catalysis; Molecular Structure; Phosphines
PubMed: 30260217
DOI: 10.1021/acs.chemrev.8b00081 -
Archives of Environmental &... 2022The aim is to assess the prevalence and knowledge on acute occupational exposure to phosphine in the shipping industry. We followed PRISMA guidelines for scoping review.... (Review)
Review
The aim is to assess the prevalence and knowledge on acute occupational exposure to phosphine in the shipping industry. We followed PRISMA guidelines for scoping review. We searched in 4 databases without language and date restrictions for scientific articles in peer-reviewed and gray literature. We found 13 peer-reviewed articles and 63 articles in gray literature. These covered 56 incidents from 1963 to 2019 for a total of 254 victims and 22 fatalities. There is an increase in the number of reported cases over the last 20 years. Neurologic and gastrointestinal symptoms are predominant, and hospitalization is needed in 80% of cases. Our review underlined the principal risk as gas exposure through leaks between holds and the ventilation system. Further studies on the knowledge and the prevention in order to improve good practices onboard, prevent the risk of fire explosion, and a global reporting system of new cases are recommended.
Topics: Naval Medicine; Occupational Exposure; Phosphines; Ships
PubMed: 34657582
DOI: 10.1080/19338244.2021.1990829 -
Advances in Colloid and Interface... Apr 2016This review summarizes everything we currently know about the nonionic surfactants alkyl dimethyl (C(n)DMPO) and alkyl diethyl (C(n)DEPO) phosphine oxide (PO... (Review)
Review
This review summarizes everything we currently know about the nonionic surfactants alkyl dimethyl (C(n)DMPO) and alkyl diethyl (C(n)DEPO) phosphine oxide (PO surfactants). The review starts with the synthesis and the general properties (Section 2) of these compounds and continues with their interfacial properties (Section 3) such as surface tension, surface rheology, interfacial tension and adsorption at solid surfaces. We discuss studies on thin liquid films and foams stabilized by PO surfactants (Section 4) as well as studies on their self-assembly into lyotropic liquid crystals and microemulsions, respectively (Section 5). We aim at encouraging colleagues from both academia and industry to take on board PO surfactants whenever possible and feasible because of their broad variety of excellent properties.
Topics: Adsorption; Oxides; Phosphines; Surface Properties; Surface-Active Agents
PubMed: 26869216
DOI: 10.1016/j.cis.2016.01.002 -
Chemistry (Weinheim An Der Bergstrasse,... Dec 2022By applying the potassium salts of cyclopentadienyl-phosphine ligands LK to CoCl , the corresponding cobalt chlorides (1, LCo Cl) were prepared. By reducing complexes 1...
By applying the potassium salts of cyclopentadienyl-phosphine ligands LK to CoCl , the corresponding cobalt chlorides (1, LCo Cl) were prepared. By reducing complexes 1 with KHBEt under a N atmosphere, bridging end-on complexes, LCo -N -Co L (2 a and 2 b), were successfully obtained. N -labeled [ N ]-2 a was prepared under N / N exchange in THF solution. LCo -N -Co L complex 2 a could react with P molecules to release N and generate a Co-P -Co moiety 4. Further reduction of complex 2 b led to cleavage of a P-C bond in the cyclopentadienyl-phosphine ligand to provide novel μ-PCy -bridged Co -N complex 5. DFT calculations confirmed the experimental observations.
Topics: Models, Molecular; Nitrogen; Phosphines; Cobalt; Ligands
PubMed: 36259370
DOI: 10.1002/chem.202202803 -
Proceedings of the Japan Academy.... 2021Metal-catalyzed asymmetric synthesis is one of the most important methods for the economical and environmentally benign production of useful optically active compounds.... (Review)
Review
Metal-catalyzed asymmetric synthesis is one of the most important methods for the economical and environmentally benign production of useful optically active compounds. The success of the asymmetric transformations is significantly dependent on the structure and electronic properties of the chiral ligands coordinating to the center metals, and hence the development of highly efficient ligands, especially chiral phosphine ligands, has long been an important research subject in this field. This review article describes the synthesis and applications of P-chiral phosphine ligands possessing chiral centers at the phosphorus atoms. Rationally designed P-chiral phosphine ligands are synthesized by the use of phosphine-boranes as the intermediates. Conformationally rigid and electron-rich P-chiral phosphine ligands exhibit excellent enantioselectivity and high catalytic activity in various transition-metal-catalyzed asymmetric reactions. Recent mechanistic studies of rhodium-catalyzed asymmetric hydrogenation are also described.
Topics: Hydrogenation; Ligands; Phosphines; Rhodium
PubMed: 34759073
DOI: 10.2183/pjab.97.026 -
Molecules (Basel, Switzerland) Jul 2022A Knoevenagel based redox-reaction promoted by intramolecular phosphine sources is presented for the first time. The influence of different diketones, aldehydes, bases...
A Knoevenagel based redox-reaction promoted by intramolecular phosphine sources is presented for the first time. The influence of different diketones, aldehydes, bases and acids was investigated. The effects of different substituents were evaluated based on their electronical influence on the diketone structure. With the obtained results a mechanism is proposed, giving information about transition states formed during the reaction, which can lead to different products. This type of an internal redox transformation with a phosphine oxide moiety remaining in the molecule after the redox reaction represents a new type of reaction.
Topics: Catalysis; Ketones; Oxidation-Reduction; Phosphines; Stereoisomerism
PubMed: 35956825
DOI: 10.3390/molecules27154875 -
Organic & Biomolecular Chemistry Apr 2022Thiols are a functional group commonly used for selective reactions in a biochemical setting because of their high nucleophilicity. Phosphorus nucleophiles can undergo...
Thiols are a functional group commonly used for selective reactions in a biochemical setting because of their high nucleophilicity. Phosphorus nucleophiles can undergo some similar reactions to thiols, but remain underexploited in this setting. In this work we show that phosphine nucleophiles react cleanly and quickly with a dehydroalanine electrophile, itself generated from cysteine, to give a stable adduct in a peptide context. NMR reveals the product to be a phosphonium ion and indicates some backbone conformational constraint, possibly arising from transient carbonyl coordination. The reaction proceeded quickly, with a pseudo-first order rate constant of 0.126 min at 1 mM peptide (80% conversion in 10 min), and with no detectable side products on the peptide. A broad peptide sequence scope and water-soluble phosphines with alkyl as well as aromatic groups were all shown to react efficiently. Phosphine addition proved to be efficient on nisin as a model Dha-containing biologically-derived peptide and on an mRNA-displayed peptide, as well as on TCEP-modified agarose for peptide capture from solution. This reaction thus presents a promising approach for modification of peptides for cargo attachment or altered physical properties in peptide discovery.
Topics: Alanine; Amino Acid Sequence; Phosphines; Sulfhydryl Compounds
PubMed: 35353113
DOI: 10.1039/d2ob00410k -
Molecules (Basel, Switzerland) May 2022α-Aminophosphonates, -phosphinates, and -phosphine oxides are a group of organophosphorus compounds that were investigated as extraction agents for rare earth (RE)... (Review)
Review
α-Aminophosphonates, -phosphinates, and -phosphine oxides are a group of organophosphorus compounds that were investigated as extraction agents for rare earth (RE) metals and actinoids for the first time in the 1960s. However, more systematic investigations of their extraction properties towards REs and actinoids were not started until the 2010s. Indeed, recent studies have shown that these α-amino-functionalized compounds can outperform the commercial organophosphorus extraction agents in RE separations. They have also proven to be very efficient extraction and precipitation agents for recovering Th and U from RE concentrates. These actinoids coexist with REs in some of the commercially important RE-containing minerals. The efficient separation and purification of REs is becoming more and more important every year as these elements have a pivotal role in many existing technologies. If one also considers the facile synthesis of α-amino-functionalized organophosphorus extractants and precipitation agents, it is expected that they will be increasingly utilized in the extraction chemistry of REs and actinoids in the future. This review collates α-aminophosphonates, -phosphinates, and -phosphine oxides that have been utilized in the separation chemistry of REs and actinoids, including their most relevant synthetic routes and molecular properties. Their extraction and precipitation properties towards REs and actinoids are also discussed.
Topics: Actinoid Series Elements; Metals, Rare Earth; Organophosphonates; Oxides; Phosphines; Thorium; Uranium
PubMed: 35684403
DOI: 10.3390/molecules27113465 -
Journal of Medicinal Chemistry Mar 2020Fungi cause serious nosocomial infections including candidiasis and aspergillosis, some of which display reduced susceptibility to current antifungals. Inorganic...
Fungi cause serious nosocomial infections including candidiasis and aspergillosis, some of which display reduced susceptibility to current antifungals. Inorganic compounds have been found to be beneficial against various medical ailments but have yet to be applied to fungal infections. Here, we explore the activity of linear and square-planar gold(I)-phosphine complexes against a panel of 28 fungal strains including spp., spp., spp., and spp. Notably, two square-planar gold(I) complexes with excellent broad-spectrum activity display potent antifungal effects against strains of , an emerging multidrug-resistant fungus that presents a serious global health threat. To characterize the biological activity of these gold(I) complexes, we used a series of time-kill studies, cytotoxicity and hemolysis assays, as well as whole-cell uptake and development of resistance studies.
Topics: Antifungal Agents; Coordination Complexes; Fungi; Gold; Humans; Microbial Sensitivity Tests; Models, Molecular; Mycoses; Phosphines
PubMed: 31841324
DOI: 10.1021/acs.jmedchem.9b01436 -
Organic Letters Oct 2020Staudinger ligation is an attractive bio-orthogonal reaction that has been widely used to tag proteins, carbohydrates, and nucleic acids. Here, we explore the traceless...
Staudinger ligation is an attractive bio-orthogonal reaction that has been widely used to tag proteins, carbohydrates, and nucleic acids. Here, we explore the traceless variant of the Staudinger ligation for 3'-end modification of oligoribonucleotides. An azido-containing dinucleotide was used to study the ligation. Nine phosphines containing reactive groups, affinity purification tags, or photoswitch probes have been successfully obtained. The corresponding modified dinucleotides were synthesized and characterized by LC/MS. Mechanistic interpretations of the reaction are proposed, in particular, the unprecedented formation of an oxazaphospholane nucleotide derivative, which was favored by the vicinal position of 2'-N and 3'-OH functional groups on the terminal ribose has been observed. The post-functionalization of a 24-nt RNA with a photoactivable tag is also reported.
Topics: Azides; Biochemical Phenomena; Carbohydrates; Molecular Structure; Phosphines; RNA
PubMed: 32996771
DOI: 10.1021/acs.orglett.0c02982