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Keywords = thiophosphonate

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14 pages, 1511 KB  
Article
Enantioseparation of P-Stereogenic 1-Adamantyl Arylthiophosphonates and Their Stereospecific Transformation to 1-Adamantyl Aryl-H-phosphinates
by Bence Varga, Levente Buna, Daniella Vincze, Tamás Holczbauer, Béla Mátravölgyi, Elemér Fogassy, György Keglevich and Péter Bagi
Molecules 2023, 28(4), 1584; https://doi.org/10.3390/molecules28041584 - 7 Feb 2023
Viewed by 1839
Abstract
A focused library of 1-adamantyl arylthiophosphonates was prepared in racemic form. An enantioseparation method was developed for P-stereogenic thiophosphonates using (S)-1-phenylethylamine as the resolving agent. Under optimized conditions, three out of the five arylthiophosphonates were prepared in enantiopure form ( [...] Read more.
A focused library of 1-adamantyl arylthiophosphonates was prepared in racemic form. An enantioseparation method was developed for P-stereogenic thiophosphonates using (S)-1-phenylethylamine as the resolving agent. Under optimized conditions, three out of the five arylthiophosphonates were prepared in enantiopure form (ee > 99%). The subsequent desulfurization of optically active arylthiophosphonates gave the corresponding H-phosphinates without significant erosion of enantiomeric purity (ee = 95–98%). Hence, this reaction sequence can be considered an alternative method for the preparation of 1-adamantyl aryl-H-phopshinates. The absolute configuration of the (S)-1-adamantyl phenylphosphonothioic acid was assigned using single-crystal XRD and it allowed the confirmation that the removal of the P = S group proceeds with retention of configuration. The organocatalytic applicability of (S)-1-adamantyl phenylphosphonothioic acid was also evaluated as a P-stereogenic Brønsted acid. Full article
(This article belongs to the Special Issue New Insights into the Preparation and Separation of Enantiomers)
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12 pages, 1335 KB  
Article
When Phosphosugars Meet Gold: Synthesis and Catalytic Activities of Phostones and Polyhydroxylated Phosphonite Au(I) Complexes
by Gaëlle Malik, Angélique Ferry and Xavier Guinchard
Molecules 2015, 20(12), 21082-21093; https://doi.org/10.3390/molecules201219755 - 27 Nov 2015
Cited by 5 | Viewed by 5660
Abstract
The synthesis and characterization of P-chiral phosphonite-, phosphonate- and thiophosphonate-Au(I) complexes are reported. These novel ligands for Au(I) are based on glycomimetic phosphorus scaffolds, obtained from the chiral pool. The catalytic activities of these complexes are shown in the cyclization of allenols and [...] Read more.
The synthesis and characterization of P-chiral phosphonite-, phosphonate- and thiophosphonate-Au(I) complexes are reported. These novel ligands for Au(I) are based on glycomimetic phosphorus scaffolds, obtained from the chiral pool. The catalytic activities of these complexes are shown in the cyclization of allenols and the hydroamination of 2-(2-propynyl)aniline combined with an organocatalyzed reduction to the corresponding 2-phenyl tetrahydroquinoline. All described gold complexes present excellent catalytic activities. Full article
(This article belongs to the Section Organometallic Chemistry)
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13 pages, 1027 KB  
Article
The Effect of Number and Position of P=O/P=S Bridging Units on Cavitand Selectivity toward Methyl Ammonium Salts
by Daniela Menozzi, Roberta Pinalli, Chiara Massera, Francesca Maffei and Enrico Dalcanale
Molecules 2015, 20(3), 4460-4472; https://doi.org/10.3390/molecules20034460 - 10 Mar 2015
Cited by 4 | Viewed by 5347
Abstract
The present work reports the synthesis and complexation properties of five mixed bridge P=O/P=S cavitands toward N,N-methyl butyl ammonium chloride (1) as prototype guest. The influence of number and position of P=O and P=S groups on the affinity of phosphonate [...] Read more.
The present work reports the synthesis and complexation properties of five mixed bridge P=O/P=S cavitands toward N,N-methyl butyl ammonium chloride (1) as prototype guest. The influence of number and position of P=O and P=S groups on the affinity of phosphonate cavitands toward 1 is assessed via ITC titrations in DCE as solvent. Comparison of the resulting Kass values, the enthalpic and entropic contributions to the overall binding with those of the parent tetraphosphonate Tiiii and tetrathiophosphonate TSiiii cavitands allows one to single out the simultaneous dual H-bond between the cavitand and the salt as the major player in complexation. Full article
(This article belongs to the Special Issue Host-Guest Chemistry)
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