Phosphorus reactions, review

The present review summarizes recent studies carried out at Princeton which have dealt with the stereochemistry of displacement reactions at phosphorus. The review is divided into two principal sections. The first part (Sect. 2) describes primarily the development of general synthetic methods for the stereospecific conversion of phosphinates -> phosphine oxides -> phosphines, and the configurational intercorrelations of these optically active organophosphorus compounds. The second part (Sect. 3) evaluates the role of pseudorotation in the stereochemistry of various displacement reactions at tetracoordinate phosphorus. The influence of steric and electronic factors is discussed with the aid of a general topological representation which maps the stereochemistry of displacement reactions at tetracoordinate centers. 

This ring is formed by acid-catalysed reaction of a 2-thiocyanatobenzoyl chloride with hydrogen chloride, or of the corresponding carboxylic acid with phosphorus pentachloride (review of this kind of reaction [2SS7]). The chlorine atom in the product is labile. 

Phosphorus heterocyclic compounds, 1, 493-538 five-membered ring systems, 1, 513-523 nomenclature, 1, 496 six-membered ring systems, 1, 497-513 Photoaromatization oxirenes from, 7, 125-126 Photobleaching chromenes in, 3, 880 Photochemical reactions heterocyclic compound synthesis from, 5, 159 reviews, 1, 56 heterocyclic compounds reviews, 1, 71, 72... 

A comprehensive review of the preparation, reactions, and n.m.r. spectra of phosphorus-fluorine compounds has appeared. This year s literature has been notable for the first detailed applications of ab initio SCF-MO calculations to the problems of bonding in halogenophosphines and their derivatives. - Comparison of the results of such theoretical calculations with experimental data obtained from photoelectron spectra shows a good correlation in the case of phosphorus trichloride and phosphoryl chloride, and of phosphorus trifluoride and its borane complex. ... 

There have apparently been no recent developments in reagents for desulphurizing sulphoxides that use pentavalent phosphorus compounds. Reagents that were reviewed in 1984 include phosphorus pentasulphide, thiophosphoryl bromide, Lawesson s reagent (1), and phosphorus pentachloride in the presence of a trap for CD ions. The traps used included an enamine or an N, JV-dialkylaniline. Presumably, the net effect of this reaction is to generate phosphorus trichloride in situ. The three thiophosphorus reagents obviously function because the P=S bond is some 150 kJ moD weaker than the P=0 bond . 

Because organophosphorus compounds are important in the chemical industry and in biology, many methods have been developed for their synthesis [1]. This chapter reviews the formation of phosphorus-carbon (P-C) bonds by the metal-catalyzed addition of phosphorus-hydrogen (P-H) bonds to unsaturated substrates, such as alkenes, alkynes, aldehydes, and imines. Section 5.2 covers reactions of P(lll) substrates (hydrophosphination), and Section 5.3 describes P(V) chemistry (hydrophosphorylation, hydrophosphinylation, hydrophosphonylation). Scheme 5-1 shows some examples of these catalytic reactions. 

The reactions of the six-membered chlorocyclophosphazene were studied with a number of aliphatic diamines (169 175), aromatic diamines (176), aliphatic diols (177-179), aromatic diols (180,181) and compounds containing amino and hydroxyl functional groups (169,170,182). This subject has been reviewed (11,16,20). There are at least five different reaction products that are possible (Fig. 19). Replacement of two chlorine atoms from the same phosphorus atom produces a spirocyclic product. Replacement of two chlorine atoms from two different phosphorus atoms in the same molecule produces an ansa product. Reaction of only one end of the difunctional reagent, resulting in the substitution of only one chlorine atom, leads to an open-chain compound. Intermolecular bridged compounds are formed when the difunc-... 

Abstract This review presents the synthesis of selected five-membered phosphorus heterocycles containing a stereogenic phosphorus in an optically active form. Their utility in a few asymmetric reactions is also briefly mentioned. 

In this chapter, synthesis, structure, and reactions of various classes of diazaphospholes have been reviewed. Recently used synthetic methods and variations for obtaining diversely substituted diazaphospholes have been discussed. On account of the cycloadditions on P=C bond of [1,4,2]- and [l,2,3]diazaphospholes, a number of organophos-phorus compounds incorporating a bridgehead phosphorus atom have become accessible. Recently reported complexation reactions of diazaphospholes, illustrate their capability to form transition metal complexes via different coordination modes. 

Reactions, under irradiation, involving the addition to unsaturated hydrocarbons of nitrogen and phosphorus compounds and of silanes have been summarized by Spinks and Woods (1990). Some cycloaddition reactions have also been reviewed. These will not be detailed here. 

Although phosphorus trisulfide (P4S6—but see below) and phosphorus pentasulfide (P4S10) have been widely used in the preparation of heterocyclic compounds there is no recent review. Weintraub has given an account of solvent- and temperature-dependent reactions of the pentasulfide, the compound employed in almost all recently reported work.118... 

Typically, intense chemiluminescence in the UV/Vis spectral region requires highly exothermic reactions such as atomic or radical recombinations (e.g., S + S + M - S2 + M) or reactions of reduced species such as hydrogen atoms, olefins, and certain sulfur and phosphorus compounds with strong oxidants such as ozone, fluorine, and chlorine dioxide. Here we review the chemistry and applications of some of the most intense chemiluminescent reactions having either demonstrated or anticipated analytical utility. 

An excellent review of steric effect of phosphorus ligands on catalytic reaction has been written by Tolman (42). 

In this chapter, we first review the nature of the several forms of elemental phosphorus and then proceed to consider their uses for specific types of syntheses of compounds containing the carbon-phosphorus bond. Prior reviews have also been concerned with these topics.1 2 Our purpose here is to update these presentations and provide fundamentals for the practicing chemist venturing into the use of elemental phosphorus. We limit this discussion to the more-or-less direct syntheses of organophosphorus compounds from elemental phosphorus. We will consider reactions that generate monophosphorus species without C-P bonds as critical intermediates, pro-... 

The use of an electron-rich trivalent phosphorus center for addition to or substitution at an electrophilic site is a long-established approach to the formation of carbon-phosphorus bonds. The classical studies of the Michaelis-Arbuzov, Michaelis-Becker, Abramov, Pudovik, and related reactions and their mechanisms and synthetic utilities have been thoroughly reviewed. In this chapter, we present only a brief introduction to these reactions and provide several examples of their more facile uses from the older literature. More attention is given to relatively recent developments regarding such reactions that are seen as improvements in their general utility. 

Virtually simultaneously with the development of the Michae-lis-Arbuzov reaction, another closely related approach toward C-P bond formation was introduced. This involved the reaction of the salts of trivalent phosphorus-centered oxyacids with the same haloal-kanes as used in the Michaelis-Arbuzov reaction. First reported by Michaelis and Becker,142 this approach is commonly known as the "Becker reaction" or the "Michaelis-Becker reaction." Fundamental aspects of this reaction system have been reviewed previously.1 2 143... 

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