Convergent-growth

In an attempt to overcome some of the problrans mcountraedin the divergent method, convergent S3mthetic routes were developed by HawkCT and Frechet. In this approach, the synthesis starts at the outside of the molecule and progresses inward, toward the core. The method is best described with reference to the original Frechet synthesis, shown below. 

This is a versatile approaeh that allows the formation of unsymmetrical structures in which wedges with different chemical compositions, i.e., different end groups, can be attached to the same core molecule. 

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J.M.J. Frechet (C. J. Hawker, 1990) replaced the divergent synthesis by a convergent growth of a dendritic polymer. The repeatedly employed monomer, 5-hydroxymethyl-l, 3-benzenediol, was 1,3-O-dibenzylatcd with 3,5-bis(benzyloxy)benzyl bromide. The resulting benzyl alcohol containing 7 benzene rings was converted to the benzyl bromide which was... 

In general, convergent methods produce the most nearly isomolecular dendrimers. This is because the convergent growth process allows purification at each step of the synthesis and therefore no cumulative effects of failed couplings are found [85, 89]. Appropriately purified convergent dendrimers are probably the most precise synthetic macromolecules that exist today. 

DOUBLE-STAGE CONVERGENT GROWTH STRATEGIES HYPERMONOMERS AND HYPERCORES... 

Preparation of Frechet-type Polyether Dendrons and Aliphatic Polyester Dendrimers by Convergent Growth An Experimental Primer... 

The convergent growth approach to dendrimers [1] first introduced [2] in 1989 at the IUPAC meeting on macromolecules in Seoul, Korea, has provided a useful alternative to the divergent methods exemplified by the work of Tomalia et al. on PAMAM dendrimers [3] and Meijer et al. on polypropylene imine) dendrimers [4], Today several hundred papers have exploited the convergent approach to dendrimers to prepare a variety of synthetic functional macromolecules of unparalleled structural precision. 

The near monodispersity typically associated with dendrimers prepared by both the divergent or convergent growth approaches presents a number of interesting characterization traits when compared to traditional narrow polydisper-sity linear polymers. These features are further enhanced by the high degree of symmetry normally associated with dendritic macromolecules and permit an unprecedented amount of structural information to be obtained using standard characterization techniques. 

As the name impHes, the core unit, or focal point group, is located at the center of the dendritic macromolecule and, as such, constitutes only a small proportion of the overall dendrimer structure. However the role of functional groups at the central core can have a profound effect on a number of physical properties and be extremely useful in investigating the structure of dendrimers. The central role played by the focal point group in the success of the convergent growth approach has also been well documented in the above discussions. 

The stepwise nature of the convergent growth approach coupled with the limited number of steps required for generation growth does however permit accu-... 

The first part of this review deals with the synthesis and characterization of dendritic aliphatic polyesters based on 2,2-bis(dimethylol)propionic acid (bis-MPA) and 1,1,1 -tris(hydroxyphenyl)ethane (THPE), as core molecule. The convergent growth approach described earlier was applied. We also present H NMR self-diffusion studies of dendrimers of first, second, and third generation. 

The chosen ABj monomer for the synthesis of die dendritic aliphatic polyesters Dl, D2, and D3 was bis-MPA. In the convergent growth approach, dendrons of certain generations were initially synthesized. In a final step these dendrons were coupled to the polyfunctional core molecule (see Scheme 2). To get an acceptable overall yield it is important that all reactions such as coupling, protection, and deprotection are selective and proceed in high yields since a laige number of steps are involved in the synthesis of the final dendrimers. 

The convergent growth approach showed to be a useful method in the synthesis of monodisperse dendrimers. The use of bis-MPA, as a building block, resulted in dendrimers with simple H NMR and NMR spectra where different generations... 

The simplest synthetic approach to the preparation of monofunctional dendritic systems is to functionalise the periphery of existing molecular scaffolds, generally constructed by divergent or convergent growth (Fig. 3.2, Route a) or b), respectively). 

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