Amino acid analogues, catalysis

Several reports have been made of a successful catalyzed addition/ substitution reaction resulting in direct attachment of phosphorus to aromatic rings. The preparation of mixed triarylphosphines has been accomplished by the reaction of tin- or silicon-substituted diphe-nylphosphines with aryl halides catalyzed by palladium reagents.74 A similar transformation has also been reported using nickel catalysis.75 The addition/substitution of diphenylphosphine to triflate functionalized phenolic linkages has been of use for the preparation of substances as analogues of tyrosine-related amino acid derivatives, accomplished with catalysis by palladium acetate (Equation 4.29).76... 

In an effort to introduce C2 symmetry into nickel complexes for their application in catalysis of asymmetric epoxidation, a series of oxocyclam analogues derived from amino acids 34 were synthesized. They did not react in the presence of PhIO as oxidant. However, they showed enhanced reactivity with NaOCl as the terminal oxidant under phase-... 

From the previous examples it is apparent that simple imprinting with a transition state analogue does not lead to cavities with sufficient catalytic activity in addition, catalytically active groups have to be placed in proper position within the cavity. This is also true for catalytic antibodies since it was shown that for, example, a guanidinium group (of the amino acid L-arginine) plays an important role in the catalysis of the basic hydrolysis of esters by a catalytic antibody. 

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