Some Organophosphorus Chemistry

Part I. The Reactions of Amines Oxidation, Reduction, Addition, Substitution, and Rearrangement Part II. Some Organophosphorus Chemistry... 

Stawinski J (1992) Some aspects of H-phosphonate chemistry. In Engel R (ed) Handbook of organophosphorus chemistry. Marcel Dekker, New York, p 377 Stawinski J, Kraszewski A (2002) Acc Chem Res 35 952... 

Interest in the chemistry of phosphines and phosphonium salts continues at a high level, and, as in previous years, considerable selection has been necessary in the preparation of this Report. A noticeable feature has been the large number of papers concerned with the preparation of chiral phosphines and their use in the homogeneous catalysis of asymmetric synthesis. Of these, only those involving some new aspect of organophosphorus chemistry are included here. 

The phase-transfer technique has been employed in the mono- and AW -di-phosphorylation of hydrazine. Full papers dealing with the preparation of acyclic and cyclic (perhydro-l,2,4,5-tetra-aza-3-phosphorine) hydrazides, a preliminary report of some of which was given in Organophosphorus Chemistry Vol. 7 (p. 114) have been published of particular interest is the formation of cage compounds (13) and (14) from monocyclic compounds by further reaction with aldehydes or ketones. 

One of the subjects of our investigations involved the interaction of allenes with the P=E derivatives. This work provided some very interesting, unexpected results that may well be of use in synthetic organophosphorus chemistry. Thus, in attempting to study the (2+2)-cycloadditions of the phosphinimine and the (methylene)phosphine systems with the allenic C=C bond, we established that the reactions take a different and more interesting course — that of an ene" reaction (eq 1). In the first step of the reaction, the electrophilic phosphorus center apparently attacks the nucleophilic central carbon of the allene system. Then, instead of undergoing nucleophilic attack on the incipient carbonium ion, the anionic center (E) abstracts a proton from the terminal C-H bond, leading to the formation of a new double bond in the phosphorus-substituted 1,3-butadiene derivatives (3). 

The articles - touching quite different aspects of organophosphorus chemistry - have been selected purposely to reflect, to some extent, the wide horizon of the subject. 

Before going on to consider some of the very valuable reactions of anhydrosulphides, both in the general context of organophosphorus chemistry and also from the viewpoint of more conventional organic synthesis, it is worth considering them briefly from the structural point of view. The so-called thionophosphine disulphides are (generally) dimeric and possess the 1,3,2,4-dithiadiphosphetane 2,4-disulphide structure. As normally prepared, the compounds exist in the trans form 207, as evidenced by X-ray analyses of, for example the 2,4-dimethyl , 2,4-diphenvl (powder structure) 2,4-bis(4-methoxyphenyl) and 2,4-bis(2,4,6-triisopropylphenyl) compounds. Evidence has been obtained which clearly demonstrates the ability of the cyclic structure to dissociate and re-form under varied con-... 

Gas-phase positive and negative ion chemistry TABLE 3. Proton affinities of some organophosphorus compounds ... 

The hydrolyses of some commercially important pesticidal phosphor-amidothioates at pH 1—11 have been measured in the case of the important compound (115), cleavage at P-S and P-0 bonds occur to approximately the same extent in DjO at 40 °C (see also Organophosphorus Chemistry , Vol. 4, p. 124, and Vol. 7, pp. 121—... 

The carbon-phosphorus analogy has been extended in different areas of organophosphorus chemistry over the last 40 years - some essential steps and consequences have been described very recently [ 13b]. Over the years, it became more and more obvious that this analogy is strengthened if the phosphorus... 

The use of the symbol R (R = simple alkyl or aryl) in carbophosphorus (organophosphorus) chemistry should always be treated with some reserve, particularly by those who are not organic chemists . Not infrequently R represents only a limited number of cases for which the quoted reaction has been demonstrated. In modern times, quite new reactions have in some cases been observed, when R represents a very bulky or a strongly electron-withdrawing group, as opposed to a simple straight chain or aromatic hydrocarbon. 

A series of seven volumes devoted to the subject of organophosphorus chemistry, completed in 19 76, lists over 100 000 compounds. It is therefore impossible to do more than touch upon some aspects which are relevant to the behaviour of the heavier elements of Group V and to organometallic chemistry as a whole. 

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. 

Coordination compounds of diphosphazane dioxides with uranyl or thorium ions were synthesized [475], The crystal structure of [U02(N03)2L1] [L, = Ph2P(0) N(Ph)P(0)Ph2] reveal the bidentate chelating mode of binding of the diphosphazane dioxide to these metals. The chemistry of other uranium organophosphorus and related compounds is described [476-479]. Some of the actinide complexes are presented in Table 5.16. 

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