Hydrolyses of Rp and Sp diastereoisomers of adenosine cyclic 3 ′, 5′-phosphoramidate (1), -N-methylphosphoramidate (2) and -N,N-dimethylphosphoramidate (3) in 0.1 N sodium hydroxide and 0.1 N hydrochloric acid, respectively, have been studied. In 0.1 N sodium hydroxide, the ester bonds of the compounds are broken. In 0.1 N hydrochloric acid, despite predictions to the contrary, _1 hydrolyzes with predominant ester bond breakings, while 3 decomposes with exclusive amide bond fission. In the acid hydrolysis of 2, cleavages of amide and ester bonds are of comparable degree. Significant differences exist between Rp and diastereo- Sp isomers. The peculiar behavior of _1 and 2 in acid hydrolysis is interpreted on the basis of ground state stereoelectronic ef fects.
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