充满生机和科学机遇的磷化学研究所

简要地综述了第十五届国际磷化学会议的报告内容，介绍了目前磷化学的主要 研究领域，包括不对称合成、配合化学，生物碱化学，药物化学，农业化学等相关 领域的研究动态及新进展。     

超分子有机膦大环化合物研究进展

有机膦大环化合物是伴随着大环化学的出现而发展起来的．它们不仅具有多变的结构而且非常稳定;不仅能够包结客体分子,还可以与许多过渡金属形成稳定的配位化合物,在主客体化学以及金属有机催化领域中受到人们的广泛关注．由于其独特的性质,有机膦大环化合物在超分子化学的发展中具有重要的地位．本文主要介绍了近些年有机膦大环化合物研究的新进展及其在超分子化学中的应用．     

低配位有机磷化学研究概况

长期以来,有机磷化学研究的核心内容主要集中在σ3和σ4的有机磷化合物及其衍生物方面,而低配位的有机磷化合物的研究则远远落后.本文简要综述了目前低配位的有机磷化合物σ1,λ1-亚膦烯、σ1,λ3-膦炔、σ2,λ3-膦烯和σ2,λ3-膦杂苯研究的最新进展,包括它们的合成及其在均相催化和材料等方面的应用.     

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.     

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。     

Aminophosphines: their chemistry and role as ligands and synthons

In recent years, research in organophosphorus chemistry has mainly focused in designing newer and better phosphorus ligands for synthesizing novel metal complexes with improved catalytic activities. Aminophosphines [tricoordinate phosphorus(III)–nitrogen systems] are considered as versatile compounds owing to the presence of nitrogen centres which, in principle, can influence additional reactivity features. They are quite sensitive to air and moisture due to the presence of polar P? N bond(s). In spite of this, research in aminophosphine chemistry is gaining momentum day‐by‐day and this is due mainly to one reason: their rich behaviour as ligands in metal complex chemistry and subsequently in catalysis. Their role as synthons in inorganic heterocyclic chemistry has also helped produce new types of heterocycles. In this paper, the chemistry of simple acyclic aminophosphines (synthesis, characterization, reactivity and applications) is covered and particular focus is given to their ability to form chalcogenides along with their role played as ligands in coordination chemistry and as synthons in inorganic heterocyclic chemistry. Copyright © 2009 John Wiley & Sons, Ltd.     

catena‐Phosphorus Cations

Recent advances towards a systematic development of catena‐phosphorus cations are reviewed. The cations represented in this new and developing chapter in fundamental phosphorus chemistry complement the series of neutral and anionic polyphosphorus compounds.     

Organocatalytic Asymmetric Synthesis of Organophosphorus Compounds

240 Years have passed since the discovery of elemental phosphorus. During that time organophosphorus chemistry has emerged as an interesting and exciting field of research. Recently organophosphorus chemistry has been raised to a new level. Organophosphorus compounds have found applications in asymmetric organocatalysis for the synthesis of optically active compounds of synthetic or biological importance. The aim of this review article is to present recent contributions to this developing field of chemistry and to point out synthetic advantages of methodologies developed so far.     

Fluorinated Derivatives of 4-Phosphino- and 4-Iminophosphorano-2,5-Dimethyl-2H-1,2,3-Diazaphospholes and Their Metal Complexes

Abstract

Although there has been considerable interest in the chemistry and metal complexation of low coordinate phosphines, there are very few examples of bisphosphine systems where both phosphorus atoms are trivalent and only one of the centers is two-coordinate^1,2. An example of such a system is the 4-phosphino-2,5-dimethyl-1,2,3-diazaphosphole obtained from acetone methylhydrazone and phosphorus trichloride³. This bisphosphine contains a two-coordinate endocyclic phosphorus and a three-coordinate exo phosphorus center. The exo phosphorus preferentially coordinates to metals but under certain conditions the two-coordinate phosphorus will also coordinate⁴.     

生命有机磷化学

简要介绍本实验室近年来在生命有机磷化学方面的研究,包括合成方法、反应机理,生命起源及分子进化和功能分子。     

质谱在生命有机磷化学中的一些应用

讨论了质谱在生命有机磷化学中的应用,包括N-磷酰氨基酸、肽、五配位磷化合物、核苷-氨基酸磷酰胺的质谱裂解途径,有机磷试剂辅助下氨基酸的自组装成肽产物和机理。     

Metal Complexes of Sulfur Ylides: Coordination Chemsistry,Preparative Organic Chemistry,and Biochemistry

In recent years both acyclic and cyclic sulfur ylides have proved to be interesting and versatile ligands in preparative organometallic chemistry. In addition to paralleling the coordination chemistry of their phosphorus analogues, sulfur ylide complexes show specific structural and chemical features; they are becoming more important in preparative inorganic and organic chemistry, and may also be biochemically relevant as methylene transfer agents. Recent studies of the complexes of the ylidic λ⁴-thiabenzenes and λ⁶-thiabenzene 1-oxides have frequently demonstrated unexpected and novel reactions, and thereby enriched the chemistry both of ylides and of carbonylmetals.     

Use of Phosphorus for Stabilizing Highly Reactive Organic Species: Nitrileimines and Pseudo-Diazoalkenes

Abstract

The synthesis and reactivity of several stable nitrile-imines bearing phosphorus groups are described. The use of stable diazomethylenephosphoranes in heterocyclic chemistry is reported.     

New Synthetic Methods for Nucleotide Analogues Based on H-Phosphonate Chemistry: A Progress Report

New synthetic methods, based on H-phosphonate chemistry, have been developed for functionalization of oligonucleotides and for the preparation of various nucleotide analogues bearing sulfur and selenium at the phosphorus center.     

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.     

Prototypical phosphorus analogues of ethane: general and versatile synthetic approaches to hexaalkylated P-P diphosphonium cations

Versatile alkylation reactions give access to symmetric, homoleptic nonsymmetric, and heteroleptic symmetric hexaalkylated 1,2-diphosphonium derivatives as bottleable salts in high yields. A series of 1,2-diphosphonium salts has been isolated and characterized, representing prototypical phosphorus analogues of ethane. Additionally, the solid-state structures for four derivatives have been determined crystallographically. Nonsymmetrically substituted derivatives of 1,2-diphosphonium cations enable the direct observation of 1J(PAPB) coupling constants for two tetracoordinate phosphorus centers. The synthetic approaches promise access to a vast array of derivatives and will provide means to the systematic development of phosphorus analogues of hydrocarbon chemistry.     

Phosphorus Compounds as Cyclization Promoted Reagents: Preparation of 1,4-α3,γ3-Diphospha-2,6-Diazines

Abstract

lmines are important classes of compounds in chemistry. In our continued investigation in the studies of the interactions betwcen group 4 (Zr, Ti) elements and main group elements we recently developped a new methodology for the preparation of various σ³, λ³ phospha-imines. Extension of this work allowed us to prepare unprecedented 8-π electron 6-membered phosphorus heterocycles; 1, 4 σ³, λ³ diphospha-2,6-diazines. The formation of these diazines involved for the first time the use of phosphorus derivatives as cyclization promoted reagents in zirconocene chemistry.     

Polyphosphorus Compounds—New Results and Perspectives

In contrast to the numerous known and often technically important mono- and diphosphorus compounds with phosphorus in its maximum oxidation state, polyphosphorus compounds led only a shadowy existence up to about twenty years ago. One of the reasons for this was the properties of such compounds, which made their handling and structural characterization difficult. This problem was solved by the development of modern preparative techniques and, especially, by the further methodological development of nuclear magnetic resonance spectroscopy. Thus, a fascinating new branch of phosphorus chemistry has been opened up in recent years. The first comprehensive review on this subject was published five years ago. Since then, research on this “element-near” chemistry of phosphorus has produced further impressive advances with the result that a surprisingly large variety of compounds with skeletons consisting of chains or rings of phosphorus atoms is known today. However, the recent observation of the spontaneous formation of the “aromatic” pentaphosphacyclopentadienide ion, P, during the synthesis of phosphorus-richer polyphosphides from phosphorus-poorer compounds in solution and the discovery of the inversion of phosphorus in tetra- and pentacyclic organophosphanes demonstrate that this field is still capable of producing surprises.     

New Phosphorus Derivatives of Salicylic Acid

Abstract

The chemistry of phosphorus derivatives of salicylic acid has been revived and the synthesis of alkadienephosphonate derivatives of salicylic acid is reported.     

Iminophosphanes: Unconventional Compounds of Main Group Elements

The large number of known stable compounds in which phosphorus has a low coordination number makes it clear that such compounds can no longer be regarded as “exotic” in main group chemistry. While the rich chemistry of P? C multiply bonded systems makes clear their affinity to their organic congeners, iminophosphanes in particular are also of increasing importance. The linkage of a phosphinidine fragment with an imine fragment via a multiple bond gives rise to a class of compounds with an unusually wide range of structural types. This in turn leads to a broad spectrum of chemical behavior which makes iminophosphanes extremely useful synthetic building blocks in organoelement chemistry.