Reports: G3
46943-G3 Investigation of O2 Activation with Metallodendrimer Models of Copper Monooxygenases
Aliphatic hydrocarbons are underutilized as chemical feedstocks because making useful derivatives requires catalysts that can oxidize C-H and C=C bonds efficiently and selectively with minimal energy requirements. Few of the numerous approaches chemists have investigated to date have produced an economically viable solution for derivation of these abundant components of crude oil. Nature has constructed a number of metalloenzymes that can oxidize unreactive bonds under mild conditions with unprecedented selectivity and high turnover numbers at rates near the diffusion limit. Researchers have constructed biomimetic coordination complexes to reproduce biological oxidation reactions with synthetic systems; however, none of these active site models exhibit catalytic chemistry reminiscent of the enzymes. We are interested in improving models for oxidation chemistry by optimizing metal-oxygen reactivity with macromolecular effects.
Scheme 1: Synthesis of Dendrimers
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The efforts during the first year on this project focused on building the necessary dendrimers to prepare the desired copper complexes. The researchers on this project have developed and refine synthetic methods for making poly(benzyl ether) dendrimers (Scheme 1). Poly(benzyl ether) dendrimers are frequently employed for catalysis because 3rd generation derivatives provide maximum dendritic encapsulation with the most facile synthesis. These aromatic dendrimers are attractive for modeling enzymatic active sites because the repeat units resemble amino acids like phenyl alanine that often form hydrophobic pockets around enzyme active sites. Despite these favorable properties, benzylic hydrogens present in these dendrimers are susceptible to abstraction by metal-bound oxygen adducts and radical species often observed in biominetic oxidations, so in our initial model complexes we tried to construct a ligand that directed the dendrimer away from the copper active site. While building ligands with to multiple dendrons branching off the ligand in close proximity to the active site may be more likely to afford models with the desired properties (Scheme 2a), we could not however, complete the construction a proof-of-concept system based on 4-aminophenol (Scheme 2b).
Scheme 2. Routes to the desired copper complexes that will be explored in year 2.
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