Content uploaded by Viktor Iaroshenko
Author content
All content in this area was uploaded by Viktor Iaroshenko on Dec 16, 2018
Content may be subject to copyright.
A preview of the PDF is not available
Organophosphorus Chemistry: From Molecules to Applications
Abstract
Filling the gap for an up-to-date reference that presents the field of organophosphorus chemistry in a comprehensive and clearly structured way, this one-stop source covers the chemistry, properties, and applications from life science and medicine. Divided into two parts, the first presents the chemistry of various phosphorus-containing compounds and their synthesis, including ylides, acids, and heterocycles. The second part then goes on to look at applications in life science and bioorganic chemistry. Last but not least, such important practical aspects as 31P-NMR and protecting strategies for these compounds are presented.
For organic, bioinorganic, and medicinal chemists, as well as those working on organometallics, and for materials scientists. The book, a contributed work, features a team of renowned scientists from around the world whose expertise spans the many aspects of modern organophosphorus chemistry.
https://www.wiley.com/en-us/Organophosphorus+Chemistry%3A+From+Molecules+to+Applications-p-9783527335725
... 1 Phosphorus is used in both its inorganic form, primarily as a fertilizer, 2, 3 and as organophosphorus compounds with a diversity of end uses including pesticides, flame retardants, plasticizers, pharmaceuticals and more. 4 The industrial synthesis of organophosphorus invariably proceeds through an energy intensive thermochemical reduction of phosphate rock to form white phosphorus (P4) which is then chlorinated to PCl3 and subsequently used as a versitile building block. 5 Both, the energy consumption and inherent danger of reactants (pyrophoric nature of P4 and toxicity of PCl3) presents problems from a sustainability perspective, as do the high temperatures (1500 o C) used for the thermochemical reduction step. ...
Organophosphorus compounds carry importance in the chemical, medical, and fertilizer industries. Their production often entails the use of white phosphorus or PCl3, which are toxic and energetically costly to produce. In this work we investigate phosphite ester formation through an electrochemical route which has the potential to serve as a greener alternative. In particular, dimethyl phosphite was electrosynthesized through oxidative coupling of an inorganic P source, H3PO2, and methanol as a model building block with high faradaic efficiencies approaching 100%. The reaction is proposed to proceed through electrooxidative phosphorus radical formation followed by coupling of this reactive species with proximal methanol molecules.
... Tertiary phosphine is one of the essential classes of chemicals that act as a reagent, catalyst, and especially as a ligand that binds to transition metals. [1] The reactivity and selectivity of related reactions are strongly influenced by the steric and electronic characteristics of phosphines. A large number of phosphines have been developed and synthesized through backbone selection and substituent groups fine-tuning on the phosphine. ...
This Concept article summarizes the main achievements in the field of synthesis of trifluoromethylphosphines through diverse methods: nucleophilic, electrophilic, and radical trifluoromethylation. Additionally, several ligand‐related applications were compiled, covering a variety of reaction types, including as a ligand in reductive elimination, asymmetric hydrogenation, and the possibility of acting as a potential trifluoromethylation reagent. image
A palladium-catalyzed regio- and stereo-selective phosphination of cyclic biarylsulfonium salts (racemic) with HPAr³Ar⁴ for straightforward synthesis of atropoisomeric phosphines (P,S-ligands) bearing a stereogenic axis or both a stereogenic axis and a P-stereogenic center is reported. The high reactivity and regio- and stereo-selectivity originate from the torsional strain release and palladium catalysis, and the construction of a P-stereogenic center is enabled by an efficient dynamic kinetic resolution. The high performance of the nascent P,S-ligands has been demonstrated in palladium-catalyzed asymmetric allylic substitutions, indicating the great potential of the present methodology.
A convenient approach towards previously unknown phosphonium salts containing a non-aromatic 2H-imidazole moiety is reported. The approach is based on a direct nucleophilic C(sp2)-H functionalization of 2H-imidazole 1-oxides with triphenylphosphine acting as a nucleophile. Herewith, the heterocyclic N-oxide moiety is utilized as an auxiliary group contributing to an abstraction of C-H proton during the elimination process. Newly obtained compounds can be a subject of further modification, e.g. used for the synthesis of monodeuterated 2H-imidazoles.
The formation of a five‐ or six‐membered ring is known to stabilize unstable molecular structures such as hemiacetals. This idea can also be extended to stabilize other high‐coordinated p‐block element species. Herein, we synthesized two novel polycyclic organophosphorus heterocycles via Staudinger‐type annulations. Reactions of either ortho‐phosphinoarenesulfonyl fluorides 1 or ortho‐phosphinobenzoic acid methyl esters 4 with ortho‐azidophenols 2 gave rise to penta‐coordinated P(V) heterocycles, benzo‐benzo‐1,2,3‐thiazaphospholo‐1,3,2‐oxazaphosphole (B‐B‐TAP‐OAP) 3 and benzo‐benzo‐1,2‐azaphospholo‐1,3,2‐oxazaphosphol‐12‐one (B‐B‐AP‐OAP) 5 in satisfactory yields. It is remarkable that heterocycles 3 and 5 are both bench‐stable and exhibit considerable stability in a 10 % aqueous tetrahydrofuran solution. Preliminary computational studies disclosed that the formation of nitrogen gas is the key driving force for the annulations. In addition, the formation of a strong Si−F bond is another contributor to the annulation of 1 and 2.
Based on phosphoryl‐substituted ynones and o‐phenylenediamines and varying reaction conditions (noncatalytic conditions or one‐pot Au‐catalyzed hydration and condensation), efficient methods for divergent synthesis of two different types of heterocyclic compounds ‐ benzo[b][1,4]diazepin‐2‐yl)phosphonates and (quinoxalin‐2‐yl)methylphosphonates‐ have been developed. image
Phosphorus exists in several different allotropes: white, red, violet and black. For industrial and academic applications, white phosphorus is the most important. So far, three polymorphs of white phosphorus, all consisting of P4 tetrahedra, have been described. Among these, β-P4 crystallizes in the space group P1 and γ-P4 in the space group C2/m. α-P4 forms soft plastic crystals with a proposed structure in the cubic space group I43m with the lattice constant a = 18.51 (3) Å, consisting of 58 rotationally disordered tetrahedra and thus is similar to the structure of α-Mn. Here we present a new polymorph, δ-P4. It crystallizes as a sixfold twin with the cell dimensions a = 18.302 (2), b = 18.302 (2), c = 36.441 (3) Å in the space group P212121 with 29 P4 tetrahedra in the asymmetric unit. The arrangement resembles the structure of α-Mn, but δ-P4 differs from α-P4. DFT calculations show δ-P4 to be metastable at a similar energy level to that of γ-P4.
ResearchGate has not been able to resolve any references for this publication.