Synthesis of phosphorus heterocycles

The use of )j2-benzyne and )j2-phosphabenzyne zirconocene in phosphorus chemistry is reviewed. The regiospecific reactions of these complexes with small unsaturated organic molecules incorporating phosphorus or not led to a variety of cyclic neutral or zwitterionic complexes showing a versatile behavior. New methodologies of synthesis of phosphorus heterocycles and of phosphorus ligands are described, as well as strategies of C-H and M-H (M=N, O, P, S) bond activations. 

Synthesis of phosphorus heterocycles via ring-closing olefin metathesis 04CRV2239. 

Dichloro(methyl)phosphane in synthesis of phosphorus heterocycles ... 

Phosphineimines in synthesis of phosphorus heterocycles 81PS(9)235. Pyrocatechol phosphorus trichloride, synthesis of and chlorinating ability ... 

F. G. Mann, working in the field since 1935, is undoubtedly the father of phosphorus as well as arsenic heterocyclic chemistry. Most of his work, mainly on saturated and benzo-annellated ring systems, is summarized in his monograph phosphorus heterocycles were made by K. Issleib and by B. A. Arbuzov, the son of... 

It will be recalled that substituted amino functions are displaced more slowly from phosphorus than halogen at low temperatures. An interesting case in the series of phosphinous halides involves the synthesis of phosphorus heterocycles having ultraviolet spectra that suggest aromatic character (46). Addition of Grignard reagents to the phos-... 

Miscellaneous. A number of reports of the synthesis of unusual heterocyclic phosphines have appeared. Improved procedures for the synthesis of l,3,5-triaza-7-phospha-adamantane (48) have been reported,40-41 and the triazaphosphahomo-adamantane (49) has also been prepared.42 Routes to the large ring phosphacyclo-alkanes (50) have been described,43 and the bicyclic diphosphine (51) has been isolated from the reaction of white phosphorus with o-dichlorobenzene in the presence of transition-metal halides.44... 

Singh R, Nolan SP (2005) Synthesis of phosphorus esters by transesterification mediated by A-heterocyclic carbenes (NHCs). Chem Comm 2005(43) 5456-5458... 

The similar endo(B)-exo cyclizations have been effected with phosphorus pentoxide and more recently with trimethylsilyl polyphosphate (equation 32 and 33). The starting alkenic oximes are readily obtainable by the alkylation of the oxime dianion. Hence the overall process provides convenient access to the stereospecific synthesis of various heterocycles bearing substituents in the desired positions. 

McReynolds, M. D., Dougherty, J. M., Hanson, P. R. Synthesis of Phosphorus and Sulfur Heterocycles via Ring-Closing Olefin Metathesis. 

The past year has seen many reports of the use of metallophosphide reagents in the synthesis of new heterocyclic phosphorus compounds... 

Equation 13 indicates an example of substitution at an sp carbon atom that has been practised in the synthesis of phosphorus-containing heterocyclic systems such as the 1,4-thiaphosphorin illustrated . 

The synthesis and reactivity of six-membered heterocycles 2-oxo- or 2-thioxo-3-sulfonyl-l,3,2-oxaphosphorinanes (190) has been described. The influence of ring size on the selectivity of phosphorus heterocycle aminolysis in the presence of water or alcohols has been investigated (Scheme 67). ... 

The aim of this Report is to review new methodology for the synthesis of saturated heterocyclic compounds. Emphasis is placed on reactions which involve a cyclization step and few ring transformations are described. Heterocycles which contain phosphorus, selenium, and silicon as the heteroatom are omitted. A few key steps in complex natural product syntheses are mentioned, but carbohydrates are excluded. The rapidly increasing numbers of reports describing the synthesis of saturated and unsaturated lactones and of crown ethers are covered in Chapters 3 and 10. 

In 1987, a new class of phosphorus heterocyclic compounds was developed by Cowley and coworkers, incorporating keto groups within various phosphorus-containing rings [37]. At the time, only the synthesis of these compounds was reported via reaction between a silylated phosphane and an acyl chloride (Scheme 12.7). More recently, we developed the diketophosphepin as a multifunctional material involving the seven-membered phosphorus ring (28a-d Figure 12.19)... 

The synthesis of phosphorus-containing heterocycles has been reported using a palladium-catalyzed approach (Scheme 4.172) [261]. The overall process involved two phosphorus-carbon(sp ) bond-forming reactions and started with a hydrophosphonylation reaction using a supported palladium catalyst to promote the addition. Conversion of the... 

The diazaphosphane or aminoiminophosphane ligands with a NPN framework are another subclass of cyclophosphazenes. These compounds with both phosphorus in oxidation state (111) [104-110] and (V) [111-112] have been employed in the synthesis of four membered heterocycles and coordination chemistry with group 13 derivatives. Several complexes of trivalent phosphorus derivatives with both aluminum halide and alkyls are known as illustrated for 48 in Scheme 21 [113-119]. The structure determination of 48 confirms the formation of a four membered metallacycle [116, 117],... 

The fourth chapter Selected Five-Membered Phosphorus Heterocycles Containing a Stereogenic Phosphorus presents the description of the synthesis and use of these compounds in a few asymmetric syntheses. 

The unique combination of double bonds in the molecules of those compounds, each with different reactivity along with the easy preparation, makes phosphorylated allenes useful substrates for the synthesis of different cyclic and noncyclic organophosphorus compounds. Recent investigations increase the scope of application of phosphorylated allenes as precursors in organic syntheses. Most of them are accompanied by the formation of five- or six-membered phosphorus heterocycles, which in many cases demonstrate certain biological activity. 

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