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Chemical Science Apr 2023An enantioselective hydrophosphination of alkenyl isoquinolines is developed by using a copper-chiral diphosphine ligand catalyst. It provides a direct and...
An enantioselective hydrophosphination of alkenyl isoquinolines is developed by using a copper-chiral diphosphine ligand catalyst. It provides a direct and atom-efficient approach to prepare a variety of chiral phosphines with an isoquinoline unit in good yields and high enantioselectivities. In addition, these chiral phosphine products are useful bidentate P,N-ligands which showed potential application in asymmetric catalysis.
PubMed: 37123192
DOI: 10.1039/d2sc06950d -
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 -
Chembiochem : a European Journal of... Sep 2022The synthesis, characterisation, and evaluation of the in vitro cytotoxicity of five maleonitriledithiolate-based ruthenium metal complexes bearing various phosphine...
The synthesis, characterisation, and evaluation of the in vitro cytotoxicity of five maleonitriledithiolate-based ruthenium metal complexes bearing various phosphine ligands towards two ovarian cancer cell lines (A2780 and A2780cisR), one non-small-cell lung cancer cell line (H460) and one normal prostate cell line (PNT2) are presented herein. These 18-electron complexes were designed with four water-soluble phosphine ligands to increase the water-solubility character of the corresponding electron-deficient ruthenium complex which showed great in vitro promises, and triphenylphosphine for comparison. The complexes with triphenylphosphine-3,3',3''-trisulfonic acid and triphenylphosphine present similar cytotoxicity compared to the 16-electron precursor, with equal cytotoxicity to both A2780 and A2780cisR. Hints at the mechanism of action suggest an apoptotic pathway based on reactive oxygen species (ROS) production. No toxicity was observed in preliminary in vivo pilot studies for these two complexes in subcutaneous A2780 and A2780cisR xenograft models, with some evidence of tumour growth delay.
Topics: Antineoplastic Agents; Carcinoma, Non-Small-Cell Lung; Cell Line, Tumor; Coordination Complexes; Drug Screening Assays, Antitumor; Female; Humans; Ligands; Lung Neoplasms; Organophosphorus Compounds; Ovarian Neoplasms; Phosphines; Reactive Oxygen Species; Ruthenium; Water
PubMed: 35838006
DOI: 10.1002/cbic.202200259 -
Angewandte Chemie (International Ed. in... Mar 2018We describe a selective and mild chemical approach for controlling RNA hybridization, folding, and enzyme interactions. Reaction of RNAs in aqueous buffer with an...
We describe a selective and mild chemical approach for controlling RNA hybridization, folding, and enzyme interactions. Reaction of RNAs in aqueous buffer with an azide-substituted acylating agent (100-200 mm) yields several 2'-OH acylations per RNA strand in as little as 10 min. This poly-acylated ("cloaked") RNA is strongly blocked from hybridization with complementary nucleic acids, from cleavage by RNA-processing enzymes, and from folding into active aptamer structures. Importantly, treatment with a water-soluble phosphine triggers a Staudinger reduction of the azide groups, resulting in spontaneous loss of acyl groups ("uncloaking"). This fully restores RNA folding and biochemical activity.
Topics: Acylation; Azides; Molecular Structure; Phosphines; RNA; RNA Folding
PubMed: 29370460
DOI: 10.1002/anie.201708696 -
Molecules (Basel, Switzerland) May 2021Phosphinic and phosphonic acids are useful intermediates and biologically active compounds which may be prepared from their esters, phosphinates and phosphonates,... (Review)
Review
Phosphinic and phosphonic acids are useful intermediates and biologically active compounds which may be prepared from their esters, phosphinates and phosphonates, respectively, by hydrolysis or dealkylation. The hydrolysis may take place both under acidic and basic conditions, but the C-O bond may also be cleaved by trimethylsilyl halides. The hydrolysis of -esters is a challenging task because, in most cases, the optimized reaction conditions have not yet been explored. Despite the importance of the hydrolysis of -esters, this field has not yet been fully surveyed. In order to fill this gap, examples of acidic and alkaline hydrolysis, as well as the dealkylation of phosphinates and phosphonates, are summarized in this review.
PubMed: 34064764
DOI: 10.3390/molecules26102840 -
Communications Chemistry Jun 2023The access to P-stereogenic motifs has always been considered a very challenging and high attractive mission in modern organic synthesis. While several chiral...
The access to P-stereogenic motifs has always been considered a very challenging and high attractive mission in modern organic synthesis. While several chiral auxiliaries employed by the practical Jugé-Stephan-like methodology have been developed, new type of readily accessible bifunctional ligands toward P-stereogenic building still remain much desirable. Herein, we present a powerful chiral template, camphor-derived 2,3-diols named CAMDOL, which were designed and synthesized from the commercially cheap camphorquinone in high yields at 50 grams scale with a column-free purification. Diverse P(III)-chiral compounds and their borane forms including phosphinous acids, phosphinites, and phosphines, as well as the corresponding P(V)-chiral compounds including phosphinates, phosphine oxides, phosphinothioates, phosphine sulfides, and secondary phosphine oxides were afforded in high yields and ee values through the optimal 2,3-diphenyl CAMDOL platform. An unusual C-OP bond cleavage following the first P-OC bond breaking was observed during the ring-opening process when quenching by NHCl solution, which generates a unique but valuable camphor-epoxide scaffold as by-product.
PubMed: 37369718
DOI: 10.1038/s42004-023-00935-0 -
Organic & Biomolecular Chemistry Dec 2014Bioorthogonal chemistry has enabled the selective labeling and detection of biomolecules in living systems. Bioorthogonal smart probes, which become fluorescent or... (Review)
Review
Bioorthogonal chemistry has enabled the selective labeling and detection of biomolecules in living systems. Bioorthogonal smart probes, which become fluorescent or deliver imaging or therapeutic agents upon reaction, allow for the visualization of biomolecules or targeted delivery even in the presence of excess unreacted probe. This review discusses the strategies used in the development of bioorthogonal smart probes and highlights the potential of these probes to further our understanding of biology.
Topics: Aldehydes; Alkynes; Azides; Click Chemistry; Cycloaddition Reaction; Drug Carriers; Fluorescence Resonance Energy Transfer; Fluorescent Dyes; Humans; Molecular Imaging; Molecular Probes; Oxidation-Reduction; Oximes; Phosphines; Staining and Labeling
PubMed: 25315039
DOI: 10.1039/c4ob01632g -
BMJ Case Reports Jun 2018
Topics: Adult; Fatal Outcome; Humans; Male; Phosphines; ST Elevation Myocardial Infarction; Zinc Compounds
PubMed: 29950357
DOI: 10.1136/bcr-2017-221457 -
Communications Chemistry Apr 2023Secondary phosphines are important building blocks in organic chemistry as their reactive P-H bond enables construction of more elaborate molecules. In particular, they...
Secondary phosphines are important building blocks in organic chemistry as their reactive P-H bond enables construction of more elaborate molecules. In particular, they can be used to construct tertiary phosphines that have widespread applications as organocatalysts, and as ligands in metal-complex catalysis. We report here a practical synthesis of the bulky secondary phosphine synthon 2,2,6,6-tetramethylphosphinane (TMPhos). Its nitrogen analogue tetramethylpiperidine, known for over a century, is used as a base in organic chemistry. We obtained TMPhos on a multigram scale from an inexpensive air-stable precursor, ammonium hypophosphite. TMPhos is also a close structural relative of di-tert-butylphosphine, a key component of many important catalysts. Herein we also describe the synthesis of key derivatives of TMPhos, with potential applications ranging from CO conversion to cross-coupling and beyond. The availability of a new core phosphine building block opens up a diverse array of opportunities in catalysis.
PubMed: 37120598
DOI: 10.1038/s42004-023-00876-8 -
International Journal of Environmental... Mar 2023Aluminum phosphide is a highly effective insecticide for fumigation in granaries and is often used in rural grain storage. However, people's awareness of its toxicity is...
Aluminum phosphide is a highly effective insecticide for fumigation in granaries and is often used in rural grain storage. However, people's awareness of its toxicity is not strong. A case of acute inhalation toxicity of phosphine caused by the use of aluminum phosphide to fumigate a granary is reported here. The case presented with aspiration pneumonia and acute left heart failure. The patient was cured using comprehensive life support treatment, including respiratory support, antiarrhythmic treatment, and blood pressure maintenance with vasoactive drugs. There is no specific antidote for phosphine poisoning at present, and the comprehensive application of restricted fluid resuscitation, high-dose glucocorticoid shock, vasoactive drugs and bedside hemofiltration is significant in improving the prognosis of patients. It is also important to remind people to pay attention to their own protection in the process of using aluminum phosphide.
Topics: Humans; Phosphines; Aluminum Compounds; Insecticides
PubMed: 36981930
DOI: 10.3390/ijerph20065021