Crown polyamines

The mucus from two other species of soapfish, Diplop-rion bifasciatum and Aulacocephalus temmninckii, contains a lipophilic ichthyotoxin, lipogrammistin A, whose stereochemistry was confirmed by total synthesis (Onuki, Tachi-bana, and Fusetani, 1993 Onuki et al, 1998). This atypical derivative contains a crown polyamine that may be unique in the animal world. 

There are some examples of macrocyclic complexes of germanium, tin and lead reported in the recent literature. Several crown ethers73,75, tetraaza macrocycles76 [for instance dibenzotetramethyltetraaza[14]annulene (TMTAA)], cyclic polyamines (polyazacycloalkanes)77-80 or, as already mentioned above, poly(pyrazolyl)borate were... 

In addition to macrocyclic hosts discussed above, many other molecules capable of selective complexation have been synthesized. They belong to so-called macrocyclic chemistry [30] encompassing crown ethers discussed in this Chapter, cryptands 61-63 [21], spherands 70 [31], cyclic polyamines 71 [32], calixarenes 18 [5], and other cyclophane cages such as 72 [33] to name but a few. Hemicarcerand 5 [2b] discussed in Chapter 1 and Section 7.3 also belongs to this domain. Typical macrocyclic host molecules are presented in Chapter 7. 

Enolase type activity is displayed in the efficient supramolecular catalysis of H/D exchange in malonate and pyruvate bound to macrocyclic polyamines [5.32]. Other processes that have been studied comprise for instance the catalysis of nucleophilic aromatic substitution by macrotricyclic quaternary ammonium receptors of type 21 [5.33], the asymmetric catalysis of Michael additions [5.34], the selective functionalization of doubly bound dicarboxylic acids [5.35] or the activation of reactions on substituted crown ethers by complexed metal ions [5.36]. 

Fig. 6.5 C3v crown structure of a stable, isolable C6(JH 8 molecule that is produced in high yield by direct hydrogenation of solid C60 (Darwish et al. 1996 Wagberg et al. 2005) and most conveniently by a polyamine hydrogenation at 200 °C in standard glassware (Briggs et al. 2005)...

Fig. 2.5. Polycyclic polyamines and macrocyclic polyamines (crown ethers) as multifunctional oil additives...

M = Ca, Sr, Ba L = glymes, crown ethers, and polyamines solvent = aliphatic or aromatic hydrocarbons) (22)... 

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