Absolute Asymmetric Synthesis 

 and Asymmetric Catalysis 



E. I. KLABUNOVSKII 



Institute of Organic Chemistry of the Academy of Sciences of the U.S.S.R., Moscozu 



It is well known that almost all substances subserving the vital activities of 

 organisms are optically active. In considering the process whereby the first 

 protein bodies came into being, one must, therefore, bear in mind the way in 

 which they became dissymmetrical, this being a necessary stage in the emergence 

 of the functions of living substance. It is clear that, once they had developed, 

 optically active compounds, having a greater free energy than racemates, would 

 quickly become commoner owing to partial asymmetric synthesis or, as they 

 act more effectively as dissymmetric catalysts, they would supplant racemates 

 in all important vital processes. The original optically active substances did not 

 arise by the action of other optically active compounds, but by absolute asym- 

 metric synthesis, owing to the action of dissymmetrical physical factors, namely 

 circularly polarized hght and asymmetric adsorption. 



A consideration of the experimental evidence set forth below shows convinc- 

 ingly the part played by the factor of dissymmetric adsorption in the production 

 of the first optically active compounds. In view of the theoretical importance of 

 absolute asymmetric synthesis for an understanding of the processes which led 

 to the production of optically active substances without the participation of 

 other optically active organic compounds we must consider both the case of 

 absolute asymmetric synthesis of optically active compounds from substances 

 of symmetrical structure, and examples of the resolution of asymmetrically 

 adsorbed racemates under the influence of the structure of the crystals on which 

 they were adsorbed. 



I. THE RESOLUTION OF RACEMATES BY 

 ASYMMETRIC ADSORPTION 



Long ago, van't Hoff [i] showed the possibihty of producing optical activity 

 in racemates by bringing them into contact with optically active substances in 

 the form of solvents, adsorbents etc. 



A number of attempts to resolve racemates of mandehc and tartaric acids [2], 

 camphor and camphorsulphonic acid and carvoxime [3] under the influence of 

 optically active fructose, Umonene and pinene, were unsuccessful. It was only 

 when the unstable racemate of 2-acetomethylamide-5 : 4-dimethyldiphenylsul- 



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