Novel high-efficiency ecologically safe electrocatalytic techniques for preparing organophosphorus compounds

Major advances and modern tendencies in electrosynthesis of organophosphorus compounds from available raw materials (mainly white phosphorus) are perused, systematized, and generalized. Potential synthetic possibilities and advantages of this intensely developing direction of elementoorganic chemistry are demonstrated.     

NEW APPROACHES TO THE SYNTHESIS OF ORGANOPHOSPHORUS COMPOUNDS

Abstract

The past two decades have brought us a snowballing development of organophosphorus chemistry. Indeed organophosphorus compounds have found wide practical application (in agriculture, petroleum industry, as drugs, etc.) and continue to afford promising objects for the study of theoretical matters such as tautomerism, ambiphilicity, ambidenticity, and other problems of organic chemistry. On the other hand, however impressive this progress may be, the search for new methods of synthesis, improving the known methods and forecasting new types of organophosphorus compounds remain as challenging problems as before.     

Recent advances in the application of sulfinic acids for the construction of sulfur-containing compounds

Sulfur-containing organic compounds display wide applications in the field of materials science, synthetic chemistry, and pharmaceutical industry. Thus, numerous synthetic strategies have been developed for the synthesis of sulfur-containing compounds in synthetic chemistry. In recent years, the utilization of sulfinic acids as versatile synthons has emerged as attractive and powerful approach to access various organosulfur compounds through sulfonylation, sulfinylation or sulfenylation reaction...     

Zirconium - Phosphorus Chemistry: Strategies in Syntheses, Reactivity, Catalysis, and Utility

Dramatic developments have taken place over the last few years in the chemistry of complexes containing Zr-P bonds and their utilization in organophosphorus chemistry. This review discusses the synthesis and reactivity of compounds containing Zr-P single and double bonds, phosphazirconacycles, and Zr complexes of substituent-free phosphorus. Applications in both stoichiometric and catalytic syntheses provide access to a variety of novel organophosphorus compounds and illustrate the potential of the organometallic approach to the synthesis of main group compounds.     

The Dawn of Functional Organoarsenic Chemistry

Organoarsenic chemistry was actively studied until the middle of 20th century. Although various properties of organoarsenic compounds have been computationally predicted, for example, frontier orbital levels, aromaticity, and inversion energies, serious concern to the danger of their synthetic processes has restricted experimental studies. Conventional synthetic routes require volatile and toxic arsenic precursors. Recently, nonvolatile intermediate transformation (NIT) methods have been developed to safely access functional organoarsenic compounds. Important intermediates in the NIT methods are cyclooligoarsines, which are prepared from nonvolatile inorganic precursors. In particular, the new approach has realized experimental studies on conjugated arsenic compounds: arsole derivatives. The elucidation of their intrinsic properties has triggered studies on functional organoarsenic chemistry. As a result, various kinds of arsenic-containing π-conjugated molecules and polymers have been reported for the last few years. In this minireview, progress of this recently invigorated field is overviewed.     

Rare‐Earth‐Metal Methylidene Complexes

Transition‐metal carbene complexes have been known for about 50 years and widely applied as reagents and catalysts in organic transformations. In contrast, the carbene chemistry of the rare‐earth metals is much less developed, but has attracted the research interest in the recent years. In this field rare‐earth‐metal alkylidene, especially methylidene, compounds are an emerging class of compounds with a high synthetic potential for organometallic chemistry and maybe in the future also for organic chemistry.     

α-Aminophosphonates, -Phosphinates,and -Phosphine Oxides as Extraction and Precipitation Agents for Rare Earth Metals,Thorium, and Uranium: A Review

α-Aminophosphonates, -phosphinates, and -phosphine oxides are a group of organophosphorus compounds that were investigated as extraction agents for rare earth (RE) metals and actinoids for the first time in the 1960s. However, more systematic investigations of their extraction properties towards REs and actinoids were not started until the 2010s. Indeed, recent studies have shown that these α-amino-functionalized compounds can outperform the commercial organophosphorus extraction agents in RE separations. They have also proven to be very efficient extraction and precipitation agents for recovering Th and U from RE concentrates. These actinoids coexist with REs in some of the commercially important RE-containing minerals. The efficient separation and purification of REs is becoming more and more important every year as these elements have a pivotal role in many existing technologies. If one also considers the facile synthesis of α-amino-functionalized organophosphorus extractants and precipitation agents, it is expected that they will be increasingly utilized in the extraction chemistry of REs and actinoids in the future. This review collates α-aminophosphonates, -phosphinates, and -phosphine oxides that have been utilized in the separation chemistry of REs and actinoids, including their most relevant synthetic routes and molecular properties. Their extraction and precipitation properties towards REs and actinoids are also discussed.     

Construction of highly substituted pyrazole derivatives with P–C bond: access to racemic and enantioselective forms by conjugate addition of diarylphosphane oxides to α,β-unsaturated pyrazolones

The synthesis of organophosphorus compounds is of great importance to industrial, agricultural, and pharmaceutical chemistry. In this paper, we have reported the synthesis of highly substituted pyrazole derivatives through P–C bond formation under catalyst-free conditions. On the other hand, the first catalytic asymmetric version of this reaction has also been developed under catalysis by an isosteviol derived thiourea organocatalyst. The optically active phosphorus-containing compounds have been obtained in good chemical yields with moderate enantioselectivities.     

Synthesis of new organophosphorus compounds using the atherton–todd reaction as a versatile tool

This article discusses the behavior of seven organophosphorus compounds under Atherton–Todd conditions. Therefore, the reactivity and selectivity of different (phen)oxaphosphinines, dioxaphosphinines, dioxaphosphinanes, and diphenylphosphine oxide with three nucleophiles were systematically studied. The results prove the versatility of the Atherton–Todd reaction to a broad range of organophosphorus compounds with different phosphorus environments and reactive P H bonds. The nucleophiles studied in this article were chosen as model substrates for amines and alcohols. Because organophosphorus molecules are important and versatile compounds, for a broad field of applications, novel synthetic approaches are of interest to both academia and industry. As an example, the single‐step synthesis of the bridged 1,3‐phenylene bis(diphenylphosphinate) with potential flame‐retardant properties was added to this study. In addition, the reaction is utilized for the synthesis of a novel organophosphorus anhydride. © 2012 Wiley Periodicals, Inc. Heteroatom Chem 23:216–222, 2012; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.21006     

Fluorescent materials based on phosphazene derivatives and their applications: Sensors and optoelectronic devices

Phosphazenes, one of the most important classes of organophosphorus compounds containing phosphorus (V) with double bonds between P and N, can be cyclic molecules or high molecular weight polymers that play an important and dominant role in advanced inorganic materials. Phosphazenes have been the subject of many studies over the past two decades as an excellent synthetic platform for the development of fluorescent materials. This study is conducted to evaluate the contribution of phosphazene chemistry to the preparation of fluorescent materials and to emphasize its importance in development of sophisticated materials. This review provides detailed information about the latest developments in the field of cyclic-, dendrimeric- and polymeric phosphazenes based fluorescent materials and their application examples of sensors (fluorescent and electrochemical) and optoelectronic devices (OLED, OFET and electrochromic devices). The future perspective of fluorescence materials based on phosphazenes is also discussed.     

Metallophosphaalkenes—from Exotics to Versatile Building Blocks in Preparative Chemistry

The chemistry of low-valent organophosphorus compounds such as phosphaalkenes and phosphaalkynes has undergone rapid development in the last two decades. This development also includes the coordination chemistry of these species, which can act as versatile ligands in metal complexes. Metallophosphaalkenes are compounds in which one or more of the organic substituents on the P?C unit is replaced by a transition metal complex fragment. Metallophosphaalkenes have emerged from an existence as laboratory curiosities to become a link between main group and organometallic complex chemistry. The great richness of their chemistry not only mirrors the specific properties of the individual building block, but also shows novel and individual traits. Particular examples are cycloadditions of these electron-rich heteroalkenes with electron-deficient alkenes, alkynes, azo, and diazo compounds. These often lead to novel types of reaction and compounds. Metallophosphaalkenes are also important as intermediates in all metal-assisted cyclooligomerizations of phosphaalkynes.     

Chirality Transfer and Memory of Chirality in Gold‐Catalyzed Reactions

Over the last few years, gold‐catalyzed reactions that involved chirality transfer and memory of chirality (MOC) have emerged as a powerful tool in enantioselective synthesis. This technique has allowed for the single‐step synthesis of enantioenriched compounds from readily available starting materials. This Focus Review discusses this emerging field with an emphasis on mechanistic aspects and their applications in synthetic organic chemistry.     

Polyvalent iodine in organic chemistry

Tricoordinate, I(III), and pentacoordinate, I(V), polyvalent iodine compounds have been known for over a century. In the last twenty years, new polyvalent iodine reagents have been introduced along with synthetic methodologies, based on these and derived reagents, that play an ever increasing role in contemporary organic chemistry. In this Perspective, an overview of these developments is provided with emphasis on the chemistry and uses of aryl-, alkenyl-, and alkynyliodonium salts in preparative and synthetic organic chemistry. It is hoped that this brief overview, along with recent more comprehensive reviews of the field, will stimulate further developments and applications of this useful class of compounds across a broad spectrum of organic chemistry.     

Design of ecologically safe and science intensive electrochemical processes

This review discusses the results of and prospects for studies aimed at design of new science intensive, environmentally safe technologies for the synthesis of organophosphorus compounds by halogenation of α-olefins, including modification of rapeseed oil; it also considers methods for the production of some other intermediates for chemical industry. New synthetic applications have been developed, using combined methods of classical organic chemistry and electrochemistry, for processes based on electrochemical generation of catalysts (mediators)—complexes of metals in low oxidation states, halogen complexes, etc. Selective electrochemical procedures are suggested for the synthesis of triphenylphosphine, trialkylphosphates, and nanosized transition metal phosphides from white phosphorus.     

Hydrogen‐Bonding Catalysis of Alkyl‐Onium Salts

The synthetic utility of alkyl‐onium salt compounds is widely recognized in the field of organic chemistry. Among the wide variety of onium salts, quaternary ammonium, phosphonium, and tertiary sulfonium salts have been the most useful compounds in organic syntheses. These compounds have been very useful reagents in the construction of organic building blocks. In addition, onium salts are known as reliable catalysts, which are used to promote important organic transformations by serving as phase‐transfer and ion‐pair catalysts through the activation of nucleophiles. Although phase‐transfer catalysis is a major direction for onium salt catalysis, hydrogen‐bonding catalysis of alkyl‐onium salts, which is promoted via the activation of electrophiles, has recently become a relevant topic in the field of onium salt chemistry. This Minireview introduces new possibilities and future directions for alkyl‐onium salt chemistry based on its use in hydrogen‐bonding catalysis and on its overall utility.     

Recent advances in the synthesis of new glycopeptide antibiotics

The vancomycin family of glycopeptide antibiotics has been inspiring research in the field of synthetic chemistry since the 1980s. Recent studies have moved away from the focus of total synthesis into new territory: the design and evaluation of novel compounds based on the natural products which exhibit improved antibacterial activity. Modern approaches to drug synthesis draw together investigations into the nature of the binding environment, and innovative synthetic methodologies which provide solutions to the challenging structural features and stereochemistry associated with this intriguing class of compounds. New analogues, derivatives and dimers of the natural products, as well as recent successes in the total synthesis of the complestatins are described in this tutorial review, covering literature from the last decade.     

有机磷化合物的电子结构与成键

本文叙述了有机磷化合物的成键与性质,以及在理论上的新发展,分下面两个内容讨论:(1)磷原子的性质与成键。(2)各类有机磷化合物的电子结构与成键。     

Phospha-organic chemistry: panorama and perspectives

Since the beginning of the seventies, organophosphorus chemistry has been completely rejuvenated by the discovery of stable derivatives in which phosphorus has the coordination numbers one or two. The chemistry of these compounds mimics the chemistry of their all-carbon analogues. In this Review article this analogy is discussed for the phosphorus counterparts of alkenes, alkynes, and carbenes. In each case, the synthesis, reactivity, and coordination modes are briefly examined. Some special electronic configurations are also discussed, which include one-electron Pbond;P bonds, strained bonds, and aromatic systems. To conclude, some potential applications of this chemistry in the areas of molecular materials and homogeneous catalysis are presented.     

Doubly charged ion mass spectra of organophosphorus compounds

Doubly charged ion mass spectra have been obtained for 11 organophosphorus compounds. Methane has been used as a target gas to increase the probability of single electron transfer collisions in the first field-free region of an Hitachi RMU-7L mass spectrometer. In general, the spectra of organophosphorus compounds do not exhibit molecular ions but are dominated by fragment ions, many of which must be formed by rearrangement processes. A geometry-optimized self-consistent field molecular orbital method has been employed to compute energies and structural parameters for prominent ions. In addition, a diabatic curve crossing model has been used to examine the single electron transfer reactions responsible for intense ions in the doubly charged ion mass spectra. Appearance energies measured for ions prominent in the 2E spectra of organophosphorus compounds have ranged from 23 to 38 eV.     

Phosphino-carboxamides: the inconspicuous gems

Compounds combining phosphine and carboxamide moieties in their molecules have developed virtually unnoticed into a specific class of highly structurally versatile and tuneable donor molecules finding manifold use in various fields, particularly in coordination chemistry, biomedical sciences and in catalysis. In the latter field, some phosphinoamides became the real privileged ligands and an indispensable part of a standard toolbox for synthetic chemists. This critical review aims to give an overview of the multifaceted chemistry of such compounds, paying attention to both the fundamentals and recent developments in this continuously expanding field.