Catenanes template synthesis

SYNTHESIS OF INTERLOCKING RINGS USING TWO DIFFERENT TRANSITION METALS AS TEMPLATING AND CONNECTING CENTERS RuCu(20.4) -", RuZn(20.4), AND RuAg(20.4) CATENANES TEMPLATE SYNTHESIS OF A 5-COORDINATE ZINC(1I) CATENANE,... 

The unlimited possibilities of designing multidentate and multitopic ligands that take advantage of the coordination geometry of specific metal ions to assemble a variety of supramolecular multinuclear architectures are far beyond the scope of this chapter, and the reader will find inspiring and fascinating examples in several reviews, as well as in other chapters of this work (see Self-Assembled Links Catenanes, Templated Synthesis of... 

Template synthesis and chirality of catenanes, rotaxanes, and pretzelanes including N-macroheterocyclic lactams and related compounds as structure components 99PAC247. 

Nonionic template synthesis of amide-linked catenanes and rotaxanes with macroheterocyclic fragments 97AG(E)930. 

Schalley CA, WeUandt T, Briiggemann J,V6gtle F (2004) Hydrogen-Bond-Mediated Template Synthesis of Rotaxanes, Catenanes, and Knotanes. 248 141-200 Scheer M,see Balazs G (2003) 232 1-23... 

R. Jager, F. Vogtle, A New Synthetic Strategy towards Molecules with Mechanical Bonds Nonionic Template Synthesis of Amide-Linked Catenanes and Rotaxanes , Angew. Chem Int. Ed. Engl. 1997,36,930-944. 

Scheme 8 Hunter and Vogtle reported independently the templated synthesis of catenanes 12 and 14... 

Scheme 10 Leigh has reported the hydrogen-bonding templated synthesis of catenane 15...

Schalley CA, Weilandt T, Briiggemann J, Vogtle F (2004) Hydrogen-bond-mediated template synthesis of rotaxanes, catenanes, and knotanes. Top Curr Chem 248 141-200... 

Figure 5.8 A single enchainment stereo isomer is obtained in the acetylcholine templated synthesis of a [2] catenane.

Hydrogen-Bond-Mediated Template Synthesis of Rotaxanes, Catenanes, and Knotanes... 

Amide-linked catenanes and rotaxanes, readily accessible via nonionic template synthesis, are molecules with fascinating topology, but their final breakthrough was only achieved when they became substrates for further chemical derivatiza-tion. A potential reaction site in the catenanes and rotaxanes presented so far is the sulfonamide group, because the proton can be selectively abstracted in the presence of carbon amide groups. Subsequent alkylation offers numerous possibilities of catenane and rotaxane chemistry. 

Fritz Vogtle Barcelona, Spain Rotaxanes, Catenanes. Pretzelanes- Template Synthesis and Chirality... 

The functionalisation also allows extending the complexity of intertwined molecular assemblies involving molecular catenanes, rotaxanes and knots. Elaborate interlocked assemblies constructed by means of metal-templation techniques and ji-ji-stacking preorganisation were reviewed [3, 11], Our last survey was devoted to the hydrogen bond templated synthesis of amide-based catenanes and rotaxanes [32], Since then a considerable advancement in elucidation of mechanisms of templation and derivatisation of the amide-based interlocked structures has been reached. Moreover, in 2000 we reported a one pot synthesis of amide-based knots such as 8 [21], which is so far the easiest preparation of molecular knots. In the following, specific possibilities of functionalisation of amide-based catenanes, rotaxanes and knots will be discussed. 

Template Synthesis of Amide-based Catenanes, Rotaxanes and Knots... 

Schalley, C.A, Reckien, W., Peyerimhoff, S., Vogtle, F. Theory and experiment in concert templated synthesis of amide rotaxanes, catenanes and knots, Chem. Eur. J. in press. 

The amide-based template synthesis of rotaxanes, catenanes and knots were first discovered by Vogtle and coworkers when they tried to synthesize macrocycle 3 [13], The cyclization to yield the tetralactam ring was carried out under high-dilution... 

A similar principle was used in the Cu(I) templated synthesis of various catenanes... 

Fig. 27. Principle of the template synthesis of a catenane. The U fragment is a metal-chelating ligand and the black dot is a transition-metal ion with a pseudo-tetrahedral coordination geometry...

Figure 2.22. Strategies for the transition metal-templated synthesis of catenanes. The metal (in) predisposes two fragments as open chelates (A) (strategy I) or as a macrocyclic chelate (E) and an open chelate (strategy II) in intermediates (B) and (F), respectively. Cyclization of these intermediate complexes with the chain fragments (C) provides the [2]-catenate complex (D).

Four donor acceptor [2]catenanes possessing cyclobis(paraquat-p-phenylene), as the 7i-electron acceptor, and 1,5-dioxynaphthalene-containing macrocyclic polyethers, as the 7i-electron donor moieties, have been constructed employing Cu+-catalyzed Huisgen 1,3-dipolar cycloaddition and Cu+2-mediated Eglinton coupling condition in the final step <07JA8236>. Desymmetrized [2]catenanes were synthesized by means of a template synthesis of pseudorotaxanes between 7i-rich crown ethers and a 7i-deficient pyromellitic subunit,... 

At present, the known catenanes can be divided into two categories - those prepared by metal template synthesis and those synthesised in the absence of a metalion influence. A considerable number of catenanes of the first type have been prepared by Sauvage et al. as well as by a number of other workers. However, discussion on these important metal-ion-directed systems is deferred to the next chapter in which particular supramolecular assemblies produced by metal-ion-controlled procedures are discussed. 

Figure 6. Synthesis of a [2]catenane templated by donor-acceptor and hydrogen bond interactions [23].

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