Phosphorus-containing macrocycles

Kyba and his coworkers have made numerous phosphorus-containing macrocycles and many of these are recorded in the tables at the end of this chapter. In addition, this group has prepared and reported quite a number of arsinocycles. The observations concerning phosphorus macrocycles apply in general to the arsinocycles as well, but the inversion barrier is even higher for the latter than the former. ... 

From Phosphorus-Containing Macrocycles to Phosphorus-Containing... 

In view of the widespread use of tertiary phosphines in coordination chemistry, it is somewhat surprising that phosphorus-containing macrocycles have not evoked more interest. In part this is undoubtedly due to experimental difficulties. The synthesis of P macrocycles is doubly difficult, since the usual difficulties and hazards of phosphorus(III) chemistry are compounded by the complexities and low yields of multistage heterocyclic macrocyclic syntheses. Because of these difficulties, the development of synthetic methods has been slow. Mann s survey73 of the heterocyclic derivatives of P, As, Sb and Bi did not mention phosphorus macrocycles and recent textbooks74,75 give them only cursory mention. 

Phosphorus-containing macrocycles, 990, 996, 998 macrocychc effect, 1002 ring size, 1003 stereochemistry, 1003 Phosphorus heterocycles transition metal complexes, 1041 Phosphorus ligands, 989-1061 ir-acid series, 1033 bonding, 1030-1041 cone angle concept, 1012 trigonal bipyramidal complexes, 1036 Phosphorus oxychloride metal complexes, 500 Phosphorus ylides transition metal complexes, 1056 Phosphorylation biological, 978 Phosvitin, 975 Photochromism... 

Phosphorus-containing macrocycles have not proved to be popnlar ligands owing, in part, to their difficult multistage synthesis. We arbitrarily define phosphorus macrocycles as those with 10 or more ring members, at least one of which is phosphorus. It should be noted that the usual purpose of... 

Phosphorus-containing macrocycles, synthesis and complexing ability of 88UK1353. 

The next two articles cover the chemistry of phosphorus containing macrocycles. The phosphorus containing cahxarenes have attracted much attention in recent years due to their various functions such as metal cations binding, catalysis, molecular recogination, and bioactivity. Likewise, other phosphorus-containing macrocycles, cryptands, and dendrimers find various uses in analytical chemistry and biochemistry. 

During the past four years, Kyba has achieved an important breakthrough in the syntheses of phosphorus-containing macrocycles.He has... 

Ciampolini et al very recently reported the synthesis of the first crown-ether-type phosphorus-containing macrocycle 4,7,13,16-tetra-... 

The basic pathways for the synthesis of phosphorus-containing macrocyclic substances are high dilution techniques and template reactions. The use of the template route enables the assembly of the triphosphine macrocyclic ligand L8, obtained as its complex with tricarbonylmolybdenum [3]. Cyclooligomerisations of molybdenum-coordinated alkenylphosphines [3] were also investigated [2], The synthesis of (CO)3Mo(L8) and (CO)3Mo(L1199) was carried out in 70-85% yield in a manner similar to that described earlier (Eq. 5.1) [3]. 

Bis(2-hydroxypropyl)(phenyl)phosphine oxide 121 is a suitable chiral precursor for the synthesis of l-phospha-ll,12-benzo-21-crown-7 123 and l-phospha-10-aza-18-crown-6 122 derivatives, the first examples of optically pure, crown-ether-like, phosphorus-containing macrocycles (Scheme 12.47). The com-plexation of Na" by the crown ether moiety of the macrocyclic ring has been observed [107]. 

Clean desulfurization of thiophosphonic macrocycles 126(X = O, Y = S) and 127 gives rise selectively to new tricoordinated phosphorus containing macrocycles 126(X = O, Y = lone pair) and 128 (Scheme 12.50). That result is of special importance taking into the account numerous types of macrocycles containing telracoordinated thiophosphonic fragments obtained by effective cyclocondensation strategy [18, 19]. 

The chemistry of phosphorus-containing macrocycles is one of the fastest developing areas of P-chemistry. The most promising compounds have been synthesized within the last two decades and applications of these classes of compounds are presently under intensive investigation. 

Caminade A-M, Majoral JP (1994) Synthesis of phosphorus-containing macrocycles and cryptands. Chem Rev 94 1183-1213... 

Prevote D, Galliot C, Caminade A-M et al (1995) Tricoordinated phosphorus-containing macrocycles new synthetic strategies. Heteroat Chem 6 313-318... 

Bauer 1, Habicher WD (1997) Synthesis of new phosphorus-containing macrocycles. Phosphorus Sulfur Silicon Relat Elem 130 89-105... 

Blokhin YI, Kornilov KN, Volchenkova YV (2009) Synthesis of unsymmetrical phosphorus-containing macrocycles on the basis of hydroquinone, 4,4 -(propane-2,2-diyl)diphenol, and resorcinol. Russ J Org Chem 45 900-903 (Zhumal Organicheskoi Khimii (2009) 45 912-915)... 

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