By Normand Voyer (auth.), F. P. Schmidtchen (eds.)

Many organic platforms nonetheless carry numerous very fascinating molecular houses that to this point can't be matched by means of manmade analogs. studying in regards to the ideas and methods utilized by nature may supply entry to novel nanostructures, more desirable catalysts for the functionalization of hydrocarbon compounds or may well let catalytic C-C bond formation below environmentally benign stipulations. This quantity recapitulates the state-of-the-art in these sectors of bioorganic chemistry that, instead of mimick the usual instance, target to make use of the underlying rules for beneficial applications.

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40a) ~~~N~ CONH-G-E-L-A-Q-K-L-E-Q-A-L-Q-K-L-A-X 48 X---NH2 49 X=-A-A-H-Y-NH2 assembling process to create a binding site for another metal by accurately orienting the imidazole groups of three histidines near the C-terminal of 49, as depicted in Fig. 18 1-42]. They showed that Cu(II) was bound in that position and that the binding process did not influence the tertiary structure. 5 Kcal/mol. In a similar way, the group of Ghadiri [43] has succeeded in preparing a well defined four ~-helix structure 50 by forming a Ru(II) complex with four pyridine-modified peptide units 51.

6 A r o m a t i c H y d r o x y l a t i o n s . . . . . . . . . . . 7 O x i d a t i o n s I n v o l v i n g H e t e r o a t o m P a r t i c i p a t i o n . . . . . 40 40 46 55 58 63 65 66 2 Active Site Analogues of Cytochrome P450 . . . . . . . 5 Introduction .............................. Thiolate Coordinating Iron Porphyrins .............. P450 A n a l o g u e s with S u b s t r a t e R e c o g n i t i o n Sites . . . . E l e c t r o n Deficient M e t a l P o r p h y r i n s ...............

3. However the formation of 11 via an acylperoxo iron(III) porphyrin has only limited significance to the enzymatic reaction, because the X-ray of cytochrome P450cam [13] revealed no acylating residue at the protein near the oxygen binding site. Moreover, this investigation, like many other discussions concerning the catalytic cycle of P450, disregards the presence of the thiolate ligand coordinating to the iron. In this context it is noteworthy that a suitable synthetic doubly bridged iron porphyrin carrying a thiolate ligand performs oxygen cleavage in the absence of an acylating agent [28], and almost certainly by homolytic O - O bond scission - see below.

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