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Organophosphorus Chemistry: A Themed Issue in Honor of Prof. Koop Lammertsma

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organic Chemistry".

Deadline for manuscript submissions: closed (31 July 2022) | Viewed by 13018

Special Issue Editor


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Guest Editor
National Insititute of Pharmaceutical Education and Research (NIPER) S.A.S. Nagar (Mohali), Punjab 160062, India
Interests: organic synthesis; medicinal chemistry; computer-aided drug design

Special Issue Information

Dear Colleagues,

Throughout his rich career, Prof. Koop Lammertsma contributed to organophosphorus chemistry with a focus on low-valent reagents, P,N-ligands, frustrated Lewis pairs, and the conversion of white phosphorus using an integrated synthetic-computational chemistry approach. This physical organic chemistry approach is also evident from his contributions in applied theoretical chemistry, carbocations, organometallics, and silicates.

He was born in Makkum, the Netherlands, and obtained his B.S. and M.Sc. at Groningen University and his Ph.D. from the University of Amsterdam. Subsequently, he joined as a PD Prof. F. Sondheimer at University College London, Prof. P. v. R. Schleyer at the University of Erlangen-Nürnberg, and Prof. G. A. Olah (Nobel Laureate, 1994) at the University of Southern California. In 1983, he moved to the University of Alabama at Birmingham, USA, and rose through the academic ranks to Professor. In 1996, he moved to the Vrije Universiteit, Amsterdam, in the Netherlands. Since 2015, he has been a Distinguished Visiting Professor at the University of Johannesburg, South Africa. He has served for both the US (NSF) and Dutch (NWO) science foundations.

Prof. Lammertsma’s many accomplishments include (i) the generation, reactivity, and organometallic chemistry of organophosphorus compounds; (ii) computational chemistry on high energy compounds (rocket propellants and explosives), carbo(di)cations, metallo­enzymes, and light-harvesting organic antennae, and (iii) chiral organosilicates.

Molecules is pleased to host a Special Issue honoring Prof. Koop Lammertsma for his outstanding achievements to advance organophosphorus chemistry and his efforts to incorporate theoretical chemistry in basic science.

Prof. Dr. Prasad V. Bharatam
Guest Editor

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Keywords

  • organophosphorus chemistry
  • computational chemistry
  • coordination chemistry

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Published Papers (5 papers)

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Research

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13 pages, 4223 KiB  
Article
Synthesis and Characterization of Phosphinecarboxamide and Phosphinecarbothioamide, and Their Complexation with Palladium(II) Complex
by Masumi Itazaki, Kento Okabayashi, Takanari Matsutani, Tomoya Nochida, Toshiyuki Moriuchi and Hiroshi Nakazawa
Molecules 2022, 27(17), 5564; https://doi.org/10.3390/molecules27175564 - 29 Aug 2022
Viewed by 1659
Abstract
Reactions of isocyanates/isothiocyanates with primary and secondary phosphines without solvent at room temperature afforded phosphinecarboxamide/phosphinecarbothioamide, respectively, in excellent yields. Furthermore, palladium complex Pd(COD)Cl2 was allowed to react with Ph2PC(O)NHPh (1a) to afford [Pd{Ph2PC(O)NHPh-κP}2 [...] Read more.
Reactions of isocyanates/isothiocyanates with primary and secondary phosphines without solvent at room temperature afforded phosphinecarboxamide/phosphinecarbothioamide, respectively, in excellent yields. Furthermore, palladium complex Pd(COD)Cl2 was allowed to react with Ph2PC(O)NHPh (1a) to afford [Pd{Ph2PC(O)NHPh-κP}2Cl2] (3). On the other hand, the reaction of Pd(COD)Cl2 with 1 eq. of Ph2PC(S)NHPh (2a) afforded [PdCl2{Ph2PC(S)NHPh-κP,S}] (4). In the case of a 1:2 molar ratio, [PdCl{Ph2PC(S)NHPh-κP,S}{Ph2PC(S)NHPh-κP}]Cl (5) was formed. The newly obtained compounds were fully characterized using multielement NMR measurements and elemental analyses. In addition, the molecular structures of Ph2PC(O)NH(CH2)2Cl (1j), Ph2PC(S)NHPh(4-Cl) (2c), and 35 were determined using single-crystal X-ray diffraction. Full article
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10 pages, 2787 KiB  
Article
Asymmetrically Substituted Phospholes as Ligands for Coinage Metal Complexes
by Fabian Roesler, Clemens Bruhn and Rudolf Pietschnig
Molecules 2022, 27(11), 3368; https://doi.org/10.3390/molecules27113368 - 24 May 2022
Viewed by 1898
Abstract
A series of coinage metal complexes asymmetrically substituted 2,5-diaryl phosphole ligands is reported. Structure, identity, and purity of all obtained complexes were corroborated with state-of-the-art techniques (multinuclear NMR, mass spectrometry, elemental analysis, X-ray diffraction) in solution and solid state. All complexes obtained feature [...] Read more.
A series of coinage metal complexes asymmetrically substituted 2,5-diaryl phosphole ligands is reported. Structure, identity, and purity of all obtained complexes were corroborated with state-of-the-art techniques (multinuclear NMR, mass spectrometry, elemental analysis, X-ray diffraction) in solution and solid state. All complexes obtained feature luminescence in solution as well as in the solid state. Additionally, DOSY-MW NMR estimation experiments were performed to achieve information about the aggregation behavior of the complexes in solution allowing a direct comparison with their structures observed in the solid state. Full article
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12 pages, 2449 KiB  
Article
1,2σ3λ3-Oxaphosphetanes and Their P-Chalcogenides—A Combined Experimental and Theoretical Study
by Florian Gleim, Antonio García Alcaraz, Gregor Schnakenburg, Arturo Espinosa Ferao and Rainer Streubel
Molecules 2022, 27(10), 3345; https://doi.org/10.3390/molecules27103345 - 23 May 2022
Cited by 1 | Viewed by 1746
Abstract
Although 1,2σ5λ5-oxaphosphetanes have been known for a long time, the “low-coordinate” 1,2σ3λ3-oxaphosphetanes have only been known since their first synthesis in 2018 via decomplexation. Apart from ligation of this P-heterocycle to gold(I)chloride and the oxidation [...] Read more.
Although 1,2σ5λ5-oxaphosphetanes have been known for a long time, the “low-coordinate” 1,2σ3λ3-oxaphosphetanes have only been known since their first synthesis in 2018 via decomplexation. Apart from ligation of this P-heterocycle to gold(I)chloride and the oxidation using ortho-chloranil, nothing on their chemistry has been reported so far. Herein, we describe the synthesis of new 1,2σ3λ3-oxaphosphetane complexes (3ae) and free derivatives (4ae), as well as reactions of 4a with chalcogens and/or chalcogen transfer reagents, which yielded the P-chalcogenides (1416a; Ch = O, S, Se). We also report on the theoretical results of the reaction pathways of C-phenyl-substituted 1,2 σ3λ3-oxaphosphetanes and ring strain energies of 1,2σ4λ5-oxaphosphetane P-chalcogenides. Full article
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13 pages, 2087 KiB  
Article
Discovery of Novel Non-Oxime Reactivators Showing In Vivo Antidotal Efficiency for Sarin Poisoned Mice
by Zhao Wei, Xinlei Zhang, Huifang Nie, Lin Yao, Yanqin Liu, Zhibing Zheng and Qin Ouyang
Molecules 2022, 27(3), 1096; https://doi.org/10.3390/molecules27031096 - 7 Feb 2022
Cited by 3 | Viewed by 2064
Abstract
A family of novel efficient non-oxime compounds exhibited promising reactivation efficacy for VX and sarin inhibited human acetylcholinesterase was discovered. It was found that aromatic groups coupled to Mannich phenols and the introduction of imidazole to the ortho position of phenols would dramatically [...] Read more.
A family of novel efficient non-oxime compounds exhibited promising reactivation efficacy for VX and sarin inhibited human acetylcholinesterase was discovered. It was found that aromatic groups coupled to Mannich phenols and the introduction of imidazole to the ortho position of phenols would dramatically enhance reactivation efficiency. Moreover, the in vivo experiment was conducted, and the results demonstrated that Mannich phenol L10R1 (30 mg/kg, ip) could afford 100% 48 h survival for mice of 2*LD50 sarin exposure, which is promising for the development of non-oxime reactivators with central efficiency. Full article
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Review

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27 pages, 6034 KiB  
Review
Friedel-Crafts-Type Acylation and Amidation Reactions in Strong Brønsted Acid: Taming Superelectrophiles
by Akinari Sumita and Tomohiko Ohwada
Molecules 2022, 27(18), 5984; https://doi.org/10.3390/molecules27185984 - 14 Sep 2022
Cited by 14 | Viewed by 4534
Abstract
In this review, we discuss Friedel-Crafts-type aromatic amidation and acylation reactions, not exhaustively, but mainly based on our research results. The electrophilic species involved are isocyanate cation and acylium cation, respectively, and both have a common +C=O structure, which can be generated [...] Read more.
In this review, we discuss Friedel-Crafts-type aromatic amidation and acylation reactions, not exhaustively, but mainly based on our research results. The electrophilic species involved are isocyanate cation and acylium cation, respectively, and both have a common +C=O structure, which can be generated from carboxylic acid functionalities in a strong Brønsted acid. Carbamates substituted with methyl salicylate can be easily ionized to the isocyanate cation upon (di)protonation of the salicylate. Carboxylic acids can be used directly as a source of acylium cations. However, aminocarboxylic acids are inert in acidic media because two positively charged sites, ammonium and acylium cation, will be generated, resulting in energetically unfavorable charge-charge repulsion. Nevertheless, the aromatic acylation of aminocarboxylic acids can be achieved by using tailored phosphoric acid esters as Lewis bases to abrogate the charge-charge repulsion. Both examples tame the superelectrophilic character. Full article
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Scheme 1

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