Strecker amino acid synthesis mechanism

This synthesis of amino acids, called the Strecker synthesis, requires the presence of NH4+ (and NH3) in the primitive ocean. On the basis of the experimental equilibrium and rate constants it can be shown16 that equal amounts of amino and hydroxy acids are obtained when the NH4+ concentration is about 0.01 M at pH 8 and 25°C with this NH4+ concentration being insensitive to temperature and pH. This translates into a pNH3 in the atmosphere of 2 x 1(U7 atm at 0° and 4 x 10-6 atm at 25°C. This is a low partial pressure, but it would seem to be necessary for amino acid synthesis. Ammonia is decomposed by ultraviolet light, but mechanisms for resynthesis are available. The details of the ammonia balance on the primitive earth remain to be worked out. 

Amino acid formation in the Urey-Miller experiment and almost certainly in the prebiotic environment is via the Stecker synthesis shown in Figure 8.3. This reaction mechanism shows that the amino acids were not formed in the discharge itself but by reactions in the condensed water reservoir. Both HCN and HCO are formed from the bond-breaking reactions of N2 and H2O in a plasma, which then react with NH3 in solution. The C=0 group in formaldehyde or other aldehydes is replaced by to form NH and this undergoes a reaction with HCN to form the cyano amino compound that hydrates to the acid. The Strecker synthesis does not provide stereo-control over the carbon centre and must result in racemic mixtures of amino acids. There is no room for homochirality in this pathway. 

The Strecker synthesis is used to prepare amino acids in the laboratory. As shown in the following equation, an aldehyde is reacted with sodium cyanide and ammonium chloride in water to produce a cyanoamine. Conversion of the cyano group to a carboxylic acid completes the synthesis. Show the structure of the intermediate, A, in the following synthesis, and show the steps in the mechanism for the formation of A and for the conversion of A to the cyanoamine. (Hint Remember that NH4+ and H,0 are in equilibrium with NH3 and H-0+.)... 

The Strecker synthesis can form a large number of amino acids from appropriate aldehydes. The mechanism is shown next. First, the aldehyde reacts with ammonia to give an imine. The imine is a nitrogen analogue of a carbonyl group, and it is electrophilic when protonated. Attack of cyanide ion on the protonated imine gives the a-amino nitrile. This mechanism is similar to that for formation of a cyanohydrin (Section 18-14), except that in the Strecker synthesis cyanide ion attacks an imine rather than the aldehyde itself. 

Miller (1953) demonstrated that the most plausible mechanism for the production of amino acids in his experiment was a Strecker or cyanohydrin synthesis. In later work it has become clear that parallel reaction pathways are possible, an addition of HCN to an aldehyde to produce the hydroxy-nitrile ... 

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