Non-covalently functionalized dendrimers

A non-covalently functionalized dendrimer was also applied in a continuous allylic amination reaction.[33] PPI dendrimers functionalized with urea adamantyl groups can act as host molecules for phosphorus ligands equipped with acetyl urea groups (Figure 4.18). The so formed supramolecular complex was reacted with a palladium precursor... 

Figure 4.19. Continuous catalysis with non-covalently functionalized dendrimers a) acid-, b) ester-functionalized guest. (Reprinted with permission from ref. 33. Copyright 2001 American Chemical Society)...

The supramolecular guest—Pd—dendrimer complex was found to have a retention of 99.4% in a CFMR and was investigated as a catalyst for the allylic ami-nation reaction. A solution of crotyl acetate and piperidine in dichloromethane was pumped through the reactor. The conversion reached its maximum ca. 80%) after approximately 1.5 h (which is equivalent to 2—3 reactor volumes of substrate solution pumped through the reactor). The conversion remained fairly constant during the course of the experiment (Fig. 8). A small decrease in conversion was observed, which was attributed to the slow deactivation of the catalyst. This experiment, however, clearly demonstrated that the non-covalently functionalized dendrimers are suitable as soluble and recyclable supports for catalysts. 

Fio. 8. Application of a non-covalently functionalized dendrimer (see fig. 7) in a CFMR in the allylic amination of crotyl acetate and piperidine in dichloromethane (Koch MPF-60 NF membrane, molecular weight cut-off = 400 Da) (21). 

In contrast to dendrimers built up from aliphatic chains, polyphenylene dendrimer micelles possess shape and size persistent cavities due to their rigid scaffold which strongly depends on the type of dendrimer. In this case a selective incorporation of guest molecules, e.g., fluorescent dyes, should be possible, dependent on the size of the guest molecule and the cavity of the host. The non-covalent uptake of dyes with an appropriate size thus allows the investigation of their interactions within the dendritic micelle. In our case we made the second-generation polyphenylene dendrimer 48, which bears 16 carboxy-functions at the periphery, by starting from a tetrahedral core and an appropriately... 

---