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Chemical Communications (Cambridge,... Sep 2020We report a proximity-driven crosslinking strategy featuring bioorthogonal cyclopropenones. These motifs react with phosphines to form electrophilic ketene-ylides. Such...
We report a proximity-driven crosslinking strategy featuring bioorthogonal cyclopropenones. These motifs react with phosphines to form electrophilic ketene-ylides. Such intermediates can be trapped by neighboring proteins to form covalent adducts. Successful crosslinking was achieved using a model split reporter, and the rate of crosslinking could be tuned using different phosphine triggers. We further demonstrated that the reaction can be performed in cell lysate. Based on these features, we anticipate that cyclopropenones will enable unique studies of protein-protein and other biomolecule interactions.
Topics: Bacteria; Biocompatible Materials; Cross-Linking Reagents; Cyclopropanes; Models, Molecular; Molecular Structure; Phosphines
PubMed: 32808608
DOI: 10.1039/d0cc04600k -
Organic Chemistry Frontiers : An... Nov 2023The development of methods for replication of synthetic information oligomers will underpin the use of directed evolution to search new chemical space. Template-directed...
The development of methods for replication of synthetic information oligomers will underpin the use of directed evolution to search new chemical space. Template-directed replication of triazole oligomers has been achieved using a covalent primer in conjunction with non-covalent binding of complementary building blocks. A phenol primer equipped with an alkyne was first attached to a benzoic recognition unit on a mixed sequence template selective covalent ester base-pair formation. The remaining phenol recognition units on the template were then used for non-covalent binding of phosphine oxide oligomers equipped with an azide. The efficiency of the templated CuAAC reaction between the primer and phosphine oxide building blocks was investigated as a function of the number of H-bonds formed with the template. Increasing the strength of the non-covalent interaction between the template and the azide lead to a significant acceleration of the templated reaction. For shorter phosphine oxide oligomers intermolecular reactions compete with the templated process, but quantitative templated primer elongation was achieved with a phosphine oxide 3-mer building block that was able to form three H-bonds with the template. NMR spectroscopy and molecular models suggest that the template can fold, but addition of the phosphine oxide 3-mer leads to a complex with three H-bonds between phosphine oxide and phenol groups, aligning the azide and alkyne groups in a favourable geometry for the CuAAC reaction. In the product duplex, H and P NMR data confirm the presence of the three H-bonded base-pairs, demonstrating that the covalent and non-covalent base-pairs are geometrically compatible. A complete replication cycle was carried out starting from the oligotriazole template by covalent attachment of the primer, followed by template-directed elongation, and hydrolysis of the the ester base-pair in the resulting duplex to regenerate the template and liberate the copy strand. We have previously demonstrated sequence-selective oligomer replication using covalent base-pairing, but the trimer building block approach described here is suitable for replication of sequence information using non-covalent binding of the monomer building blocks to a template.
PubMed: 38022796
DOI: 10.1039/d3qo01717f -
Chemical Science Apr 2022The catalytic asymmetric synthesis of -stereogenic phosphines is an efficient strategy to access structurally diverse chiral phosphines that could serve as...
The catalytic asymmetric synthesis of -stereogenic phosphines is an efficient strategy to access structurally diverse chiral phosphines that could serve as organocatalysts and ligands to transition metals and motifs of antiviral drugs. Herein, we describe a Ni catalyzed highly regio and enantioselective hydrophosphinylation reaction of secondary phosphine oxides and enynes. This method afforded a plethora of alkenyl phosphine oxides which could serve as valuable precursors to bidentate ligands. A new type of mechanism was discovered by combined kinetic studies and density functional theory (DFT) calculations, which was opposed to the widely accepted Chalk-Harrod type mechanism. Notably, the alkene moiety which could serve as a directing group by coordinating with the Ni catalyst in the transition state, plays a vital role in determining the reactivity, regio and enantioselectivity.
PubMed: 35440997
DOI: 10.1039/d2sc00091a -
Advanced Science (Weinheim,... May 2022Atomically precise gold clusters are highly desirable due to their well-defined structure which allows the study of structure-property relationships. In addition, they... (Review)
Review
Atomically precise gold clusters are highly desirable due to their well-defined structure which allows the study of structure-property relationships. In addition, they have potential in technological applications such as nanoscale catalysis. The structural, chemical, electronic, and optical properties of ligated gold clusters are strongly defined by the metal-ligand interaction and type of ligands. This critical feature renders gold-phosphine clusters unique and distinct from other ligand-protected gold clusters. The use of multidentate phosphines enables preparation of varying core sizes and exotic structures beyond regular polyhedrons. Weak gold-phosphorous (Au-P) bonding is advantageous for ligand exchange and removal for specific applications, such as catalysis, without agglomeration. The aim of this review is to provide a unified view of gold-phosphine clusters and to present an in-depth discussion on recent advances and key developments for these clusters. This review features the unique chemistry, structural, electronic, and optical properties of gold-phosphine clusters. Advanced characterization techniques, including synchrotron-based spectroscopy, have unraveled substantial effects of Au-P interaction on the composition-, structure-, and size-dependent properties. State-of-the-art theoretical calculations that reveal insights into experimental findings are also discussed. Finally, a discussion of the application of gold-phosphine clusters in catalysis is presented.
PubMed: 35332703
DOI: 10.1002/advs.202105692 -
Chemistry (Weinheim An Der Bergstrasse,... Aug 2021A library of gold(I) chloride complexes with phosphine ligands incorporating pendant (thio)urea and squaramide H-bond donors was prepared with the aim of promoting...
A library of gold(I) chloride complexes with phosphine ligands incorporating pendant (thio)urea and squaramide H-bond donors was prepared with the aim of promoting chloride abstraction from Au(I) via H-bonding. In the absence of silver additives, complexes bearing squaramides and trifluoromethylated aromatic ureas displayed good catalytic activity in the cyclization of N-propargyl benzamides, as well as in a 1,6-enyne cycloisomerization, a tandem cyclization-indole addition reaction and the hydrohydrazination of phenylacetylene. Kinetic studies and DFT calculations indicate that the energetic span of the reaction is accounted by both the chloride abstraction step, facilitated by the bidentate H-bond donor via an associative mechanism, and the subsequent cyclization step.
Topics: Catalysis; Kinetics; Ligands; Phosphines; Quinine; Silver; Urea
PubMed: 34018646
DOI: 10.1002/chem.202101751 -
Polymers Oct 2023A new set of microporous organic polymers (POPs) containing diphosphine derivatives synthesized by knitting via Friedel-Crafts has been attained. These amorphous...
A new set of microporous organic polymers (POPs) containing diphosphine derivatives synthesized by knitting via Friedel-Crafts has been attained. These amorphous three-dimensional materials have been prepared by utilizing diphosphines, 1,3,5-triphenylbenzene, and biphenyl as nucleophile aromatic groups, dimethoxymethane as the electrophilic linker, and FeCl as a promoting catalyst. These polymer networks display moderate thermal stability and high microporosity, boasting BET surface areas above 760 m/g. They are capable of coordinating with palladium acetate, using the phosphine derivative as an anchoring center, and have proven to be highly efficient catalysts in Suzuki-Miyaura coupling reactions involving bromo- and chloroarenes under environmentally friendly (using water and ethanol as solvents) and aerobic conditions. These supported catalysts have achieved excellent turnover numbers (TON) and turnover frequencies (TOF), while maintaining good recyclability without significant loss of activity or Pd leaching after five consecutive reaction cycles.
PubMed: 37896387
DOI: 10.3390/polym15204143 -
Insects Oct 2023Knowledge about resistance mechanisms can provide ideas for pesticide resistance management. Although several studies have unveiled the positive or negative impacts of...
Knowledge about resistance mechanisms can provide ideas for pesticide resistance management. Although several studies have unveiled the positive or negative impacts of gut microbes on host pesticide resistance, minimal research is available regarding the association between gut microbes and host phosphine resistance. To explore the influence of gut bacteria on host phosphine susceptibility and its molecular basis, mortality, fitness, redox responses, and immune responses of adult were determined when it was challenged by phosphine exposure and/or gut bacteria inoculation. Five cultivable gut bacteria were excised from a population of phosphine-resistant . . Among them, only sp. inoculation significantly promoted host susceptibility to phosphine, while inoculation of any other gut bacteria had no significant effect on host phosphine susceptibility. Furthermore, when . was exposed to phosphine, sp. inoculation decreased the female fecundity, promoted host oxidative stress, and suppressed the expression and activity of host superoxide dismutase, catalase, and peroxidase. In the absence of phosphine, sp. inoculation also elicited overactive immune responses in . , including the immune deficiency and Toll signaling pathways and the dual oxidase-reactive oxygen species system. These results indicate that sp. likely promotes host phosphine susceptibility by aggravating oxidative stress and fitness costs.
PubMed: 37887827
DOI: 10.3390/insects14100815 -
ACS Applied Materials & Interfaces Jun 2023Effective strategies for the detection and identification of explosives are highly desirable. Herein, we illustrate the efficient optoelectronic detection of...
Effective strategies for the detection and identification of explosives are highly desirable. Herein, we illustrate the efficient optoelectronic detection of nitroaromatic and peroxide-based explosives using amine- and phosphine-substituted diketopyrrolopyrroles. Selective quenching and an unprecedented enhancement of thin-film emission in the presence of nitroaromatic vapors are demonstrated the judicious choice of amine substituents. The modulation of fluorescence emission in each case is shown to be dominated by electronic and thermodynamic effects, the vapor pressure of explosives, and the thin-film morphology. For peroxide detection, we describe an approach exploiting redox-mediated functional group transformation. The rapid oxidation of triphenylphosphine to phosphine oxide with hydrogen peroxide affords a significant increase in fluorescence emission, facilitating the sensitive turn-on detection of an important class of explosives at ppb concentrations.
PubMed: 37255311
DOI: 10.1021/acsami.3c02714 -
Molecules (Basel, Switzerland) Jan 2021Dendrimers are hyperbranched macromolecules, which are synthesized step-by-step by the repetition of a series of reactions. While many different types of dendrimers are... (Review)
Review
Dendrimers are hyperbranched macromolecules, which are synthesized step-by-step by the repetition of a series of reactions. While many different types of dendrimers are known, this review focusses on the use of trivalent phosphorus derivatives (essentially phosphines and phosphoramidites) for the synthesis of dendrimers. The first part presents dendrimers constituted of phosphines at each branching point. The other parts display the use of trivalent phosphorus derivatives during the synthesis of dendrimers. Different types of reactions have been applied to phosphines. The very first examples of phosphorus-containing dendrimers were obtained by the alkylation of phosphines. Then, several families of dendrimers were elaborated by reaction of phosphoramidites. Such a type of reaction is the base of the solid phase synthesis of oligonucleotides; it has been applied in particular for the synthesis of dendrimers constituted of oligonucleotides. Finally, the Staudinger reaction between phosphines and azides afforded different families of dendrimers, and was at the origin of accelerated methods of synthesis of dendrimers. Besides, the reactivity of the P=N-P=S linkages created by this reaction led to very original dendritic structures.
Topics: Alkylation; Chemistry Techniques, Synthetic; Dendrimers; Molecular Structure; Organophosphorus Compounds; Phosphines; Phosphorus
PubMed: 33430439
DOI: 10.3390/molecules26020269 -
Frontiers in Chemistry 2023Organophosphorus esters fulfil many industrial, agricultural, and household roles. Nature has deployed phosphates and their related anhydrides as energy carriers and... (Review)
Review
Organophosphorus esters fulfil many industrial, agricultural, and household roles. Nature has deployed phosphates and their related anhydrides as energy carriers and reservoirs, as constituents of genetic materials in the form of DNA and RNA, and as intermediates in key biochemical conversions. The transfer of the phosphoryl (PO) group is thus a ubiquitous biological process that is involved in a variety of transformations at the cellular level such as bioenergy and signals transductions. Significant attention has been paid in the last seven decades to understanding the mechanisms of uncatalyzed (solution) chemistry of the phospho group transfer because of the notion that enzymes convert the dissociative transition state structures in the uncatalyzed reactions into associative ones in the biological processes. In this regard, it has also been proposed that the rate enhancements enacted by enzymes result from the desolvation of the ground state in the hydrophobic active site environments, although theoretical calculations seem to disagree with this position. As a result, some attention has been paid to the study of the effects of solvent change, from water to less polar solvents, in uncatalyzed phospho transfer reactions. Such changes have consequences on the stabilities of the ground and the transition states of reactions which affect reactivities and, sometimes, the mechanisms of reactions. This review seeks to collate and evaluate what is known about solvent effects in this domain, especially their effects on rates of reactions of different classes of organophosphorus esters. The outcome of this exercise shows that a systematized study of solvent effects needs to be undertaken to fully understand the physical organic chemistry of the transfer of phosphates and related molecules from aqueous to substantially hydrophobic environments, since significant knowledge gaps exist.
PubMed: 37179775
DOI: 10.3389/fchem.2023.1176746