Biomimetic catalysis

B. S. Green, Y. Ashani, and D. Chipman, eds.. Chemical Approaches to Understanding En me Catalysis Biomimetic Chemistry and Transition State Analogs, Elsevier, Amsterdam, 1982. 

Popovitz-Biro, R. Chang, H. C. Tang, C. P. Shochet, N. Lahav, M. Leiserowitz, L. In Chemical Approaches to Understanding Enzyme Catalysis Biomimetic Chemistry and Transition-State Analogs Green, B. S. Ashani, Y. Chipman, D., Eds. Elsevier Amsterdam, 1982, pp. 88-105. 

G. Wulff and A. Sarhan, In Chemical approaches to understanding enzyme catalysis biomimetic chemistry and transition state analogs, B.S. Green, Y. Ashani and D. Chipman Eds, Elsevier, Amsterdam, p. 106 (1982). 

Similar to enzymatic catalysis, biomimetic catalysis offers high selectivity and efficiency. Biomimetic synthesis and the closely related cascade reaction techniques have great potential for accomplishing the goals of Green Chemistry that is beginning to be resized. 

In this chapter we summarize key molecular concepts in biocatalysis and compare them with the molecular understanding of reaction mechanisms in heterogeneous catalysis that was developed in the previous chapters. The first four sections of this chapter emphasize enzyme catalysis. Biomimetic approaches are described in later sections. 

As an approach to biomimetic catalysis, Sanders and colleagues [67] synthesized a series of 1,1,2-linked cyclic porphyrin trimers that allow the stereo- and regiochemistry of the Diels-Alder reaction of 84 and 85 within the molecular cavity to be controlled, thereby producing prevalently or exclusively the endo 86 or the exo 87 adduct. Two examples are illustrated in Scheme 4.18. At 30 °C and in the absence of 88, the reaction furnishes a mixture of diastereoisomers, while the addition of one equivalent of trimer 88 accelerates the reaction 1000-fold and the thermodynamically more stable exo adduct 87 is the sole detectable product. 

At the present time, "interest in reversed micelles is intense for several reasons. The rates of several types of reactions in apolar solvents are strongly enhanced by certain amphiphiles, and this "micellar catalysis" has been regarded as a model for enzyme activity (. Aside from such "biomimetic" features, rate enhancement by these surfactants may be important for applications in synthetic chemistry. Lastly, the aqueous "pools" solubilized within reversed micelles may be spectrally probed to provide structural information on the otherwise elusive state of water in small clusters. 

So far, certain biomimetic catalysts (1 and 2b in Fig. 18.17) have been shown to reduce O2 to H2O under a slow electron flux at physiologically relevant conditions (pH 7,0.2-0.05 V potential vs. NHE) and retain their catalytic activity for >10" turnovers. Probably, only the increased stability of the turning-over catalyst is of relevance to the development of practical ORR catalysts for fuel cells. In addition, biomimetic catalysts of series 1,2,3, and 5, and catalyst 4b are the only metalloporphyrins studied in ORR catalysis with well-defined proximal and distal environments. For series 2, which is by far the most thoroughly studied series of biomimetic ORR catalysts, these well-defined environments result in an effective catalysis that seems to be the least sensitive among all metalloporphyrins to the electrode material (whether the catalyst is adsorbed or in the film) and to chemicals present in the electrolyte or in the O2 stream, including typical catalyst poisons (CO and CN ). 

Diversity-Based Approaches to Selective Biomimetic Oxidation Catalysis Albrecht Berkessel... 

Bob s research interests and knowledge across chemistry were great. Throughout his career he retained an interest in biomimetic chemistry, specifically the study of metal ion-promoted reactions and reactions of molecules activated by metal ion coordination. His early interests in carbohydrate chemistry inspired him to study metal ion catalysis of both peptide formation and hydrolysis as well as studies in inorganic reaction mechanisms. He was particularly interested in the mechanisms of base-catalyzed hydrolysis within metal complexes and the development of the so-called dissociative conjugate-base (DCB) mechanism for base-catalyzed substitution reactions at inert d6 metal ions such as Co(III). 

See for example the pioneering work of Breslow Bres-low, R. Dong, S. D. Biomimetic Reactions Catalyzed by Cyclodextrins and their Derivatives Chem. Rev. 1998, 98,1997-2011 and Breslow, R. Biomimetic Chemistiy and Artificial Enzymes - Catalysis by Design Acc Chem. Res. 1995,28,146-153. 

As discussed in the first section of this chapter, interest in dendrimers has increased rapidly since the successful synthesis of the first cascade molecules two decades ago. Much of this interest has been driven by the expectation that dendrimers will exhibit unique properties [2-5, 60]. Because dendrimers in many cases interact strongly with metal ions, it seems reasonable to expect that such composite materials might provide additional heretofore unknown or biomimetic functions. This is particularly true in hght of the high number of metal ions that can be complexed to a single dendrimer and (in some cases) their well-defined position in the dendrimer. For example, there has been much recent speculation that these materials will be useful for catalysis [3, 4, 53,... 

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