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Complete Kinetic Analysis of the Thermal Stereomutations of (+)-(1S,2S,3R)-r-1-Cyano-t-2-methyl-1,2,t-3-trideuteriocyclopropane
Baldwin, John E.,Carter, Charles G.
, p. 1362 - 1368 (2007/10/02)
(+)-(1S,2S,3R)-r-1-Cyano-t-2-methyl-1,2,t-3-trideuteriocyclopropane has been synthesized in optically pure form.The kinetic of thermal stereomutations which interconvert this and seven other isomeric cyclopropanes have been followed: at 335.4 deg C in the gas phase, the title compound undergoes stereomutations with rate constants (x105 s) k1 = 0.55, k2 = 0.61, k3 = 0.10, k12 = 0.88, k13 = 0.083, and k23 = 0; the cis-1-cyano-2-methyl-1,2,3-trideuteriocyclopropanes exhibit stereomutation rate constants (x105 s) k'1 = 0.62, k'2 = 0.69, k'3 = 0.15, k'12 = 1.31, k'13 = 0.09, and k'23 = 0.While cyclopropanes 1,2-disubstituted with potent radical-stabilizing groups such as phenyl, cyano, and vinyl give stereomutation products by way of C(1)-C(2) bond cleavage only, the deuterium-labeled 1-cyano-2-methylcyclopropanes experience thermal stereomutations consistent with the intermediacy of two distinct trimethylene diradicals, one formed through cleavage of the C(1)-C(2) bond, the other by breaking C(1)-C(3).
