Stereochemical Kinetics of the Thermal Stereomutations of 1-Cyano-2-phenyl-1,3-dideuteriocyclopropanes

Article abstract of DOI:10.1021/jo00170a008

A complete kinetic analysis of the stereomutations that interconvert the isomers of 1-cyano-2-phenyl-1,3-dideuteriocyclopropane at 242.1 deg C has been attained by following the thermolysis of (+)-(1S,2S,3S)-r-1-cyano-t-2-phenyl-1,c-3-dideuteriocyclopropane and its stereoisomers.The kinetic parameters describing the time evolution of the set of eight isomers are K_eq(cis/trans) = 0.40 and rate constants (x10⁵ s) k₁ = 0.76, k₂ = 0.33, k₁₂ = 0.60, k'₁₂ = 0.43; k₁₃, k₂₃, k₃, and k'₃ are all found to be zero.In this system, and in contrast to results obt ained for the 1-cyano-2-methyl-1,2,3-trideuteriocyclopropanes and the 2,3-dideuterio-2-(methoxymethyl)spiro, all stereomutations may be rationalized in terms of C(1)-C(2) bond cleavage.