Supramolecular assistance

One may imagine extending this type of methodology to reactivity, catalysis and transport by generating suitable libraries for the discovery of novel synthetic reagents, reactions, catalysts [9.176c] and carriers as well as for the exploration of product preparation through supramolecular assistance to synthesis (see Section 9.6). 

One may expect that by taking advantage of suitably designed supramolecular features it will be possible to generate a variety of highly complex architectures that would not be accessible otherwise (or only with low efficiency). Such supramolecular assistance adds a new direction with powerful means to organic synthesis. 

SUPRAMOLECULAR ASSISTANCE IN REACTIONS DISPLAYING CHIRAL INDUCTION... 

During the past 20 years, mechanically interlocked molecules, known as catenanes and rotaxanes, many of them redox-active, have become readily accessible using template-directed protocols that rely upon the precepts of molecular recognition and self-assembly and the tenets of supramolecular assistance to covalent synthesis. By incorporating different recognition units with dissimilar redox properties into appropriate components, these compounds can often be induced to switch hysteretically between ground and metastable co-con-... 

Supramolecular assistance to covalent synthesis has become an important tool as an alternative synthetic route to prepare stereocontrolled compounds either in solution or in the solid state. Chemical synthesis performed in the solid state provides an interesting green alternative for the preparation of novel and traditional products. ... 

Another aspect of synthetic supramolecular chemistry is the supramolecular assistance to molecular synthesis, in which intermolecular non-covalent interactions are used to bring molecular components in appropriate position and orientation in the intermediate steps of the synthesis of a molecular compound [17]. In both these aspects the self-assembly is the main actor [32-34]. 

Using the Supramolecularly Assisted Method Followed by Covalent Bond Formation... 

Kim, S.H., Nederberg, E, Jakobs, R. et al. (2009b) A Supramolecularly assisted transfmmation of block-copolymer micelles into nanotubes. Angewandte Chemie-Intemational Edition, 48,4508-4512. 

The self-assembled monolayers (SAM) are prepared by chemically linking ordered rigid molecules to complementary sites on a solid surface. Examples are described in this volume in Chapter 10 (cf. also Section in.D). The topochemical polymerization of diacetylenes should also be regarded as a supramolecularly assisted process requiring very specific arrangements of the monomers within the crystalline state [35]. 

Table 2 Comparison of % Shell Filling as a Function of Core and Shell Dendrimers, Using the Supramolecularly Assisted Method Followed by Covalent Bond Formation...

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