MACROCYCLIC POLY AMINES

MACROCYCLIC POLY AMINES, 58, 86, 90 MACROLIDES, 58, 98 Magnesium, bromo phenyl, 58, 138 Magnesium methyl carbonate, 56, 121 Maleic acid, methyl ester, 56, 63 Manganese, tricarbonyl[(l,2,3,4,5-7))-l-carboxy-2,4-cyclopentadien 1 yl], ... 

Macrocyclic derivatives are of considerable importance in biological areas and as complexing agents, particularly for metals. Macrocyclic examples are given in MACROLIDES FROM CYCLIZATION OF w-BROMOCARBOXYLIC ACIDS 11-HYDROXYUNDECANOIC LACTONE and MACROCYCLIC POLY AMINES 1,4,7,10,13,16-HEX AAZ ACYCLOOCT ADE-... 

Macrocyclic poly amines as biological cation and anion complexones — an application to calculi dissolution. E. Kimura, Top. Curr. Chem., 1985,128,113 (85). 

Receptors for anions vary widely, and are in many instances either the same or modified versions of the ligands that bind transition metal ions [5-20], For example, poly amine macrocycles can bind transition metal ions, while poly ammonium macrocycles bind anions. In many instances the same ligand can bind either a transition metal ion [21-24] or an anion [25-29],... 

To synthesize macrocycles in good yields, the reactions of di(3-bromobenzene)polyamines 12 with corresponding poly amines 2 were run in the presence of a double amount amount of catalyst (16 mol%), in dilute dioxane solutions, and in the majority of cases corresponding cyclodimers were formed in reasonable to good yields (up to 44%). 

The problem of isolation and purification of bis(polyamine)-substituted pyridines 21 was found to be quite serious and we decided to use them in situ in the synthesis of eyelodimers, producing them from 1 equiv. of dibromide and 4 equiv. of polyamine to minimize possible excess of polyamines which would lead to macrocycles and not to cyclodimers. Following the method (A), eyelodimers 22a,fj,l,m were synthesized by the reaction of bis(halopyridinyl)-substituted poly amines 17a and 19a,fj with polyamines 2a,fj (Scheme 10). 

This review presents the syntheses of different analogs of sucrose. Transformations of this di-saccharide at the terminal positions (Cl, or C6, or C6 ) provide modified sucroses such as amines, uronic acids, thiols, or phosphorus derivatives. Preparation of so-called higher sucroses i.e. derivatives in which the terminal positions are elongated by a poly-hydroxylated carbon chain is also reviewed. Special attention is directed to the synthesis and properties of macrocyclic derivatives crown- and aza-crown ethers with sucrose scaffold. Such macrocyclic receptors exhibit interesting complexing properties towards chiral ammonium salts. 

Analogously, the aspartie protease inhibitor 228 (Figure 11.17, site of reaction and reducing reagent indieated) was constructed via an intramolecular reductive amination. In addition, multiple reductive amina-tions can be applied to assemble molecules such as the symmetrical G-quadruplex macrocyclic ligand BOQl (229) and antiprotozoal poly-azamacrocycles such as 230. For the latter, an iron (II) complex was employed as an intermediate to assist with the ring closure. 

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