115373-63-2Relevant academic research and scientific papers
The Contribution of Ring Strain to Nucleofugality: the First Measurement
Griffiths, Gwerydd,Hughes, Simon,Stirling, Charles J. M.
, p. 236 - 237 (1982)
Comparison of eliminative ring fission in a cyclopropane and elimination in an acyclic analogue allows determination of acceleration of elimination by ring strain; a factor of at least 1011.7 has been found, the largest for any heterocyclic reaction.
Reaction of cyclopropylcarbene-metal complexes with nucleophiles, halogens and HX
Reid, Margaret D.,Tirado, Liz,Zhang, Jianwei,Dike, Nwamara,Herndon, James W.
, p. 5759 - 5776 (2007/10/03)
The reaction of halogens, pseudohalogens, and HX with cyclopropyl(phenylthio)carbene-chromium complexes leads to the formation of 1,4-dihalo-1-thiophenyl-1-butene systems with a moderate-high degree of stereocontrol in the formation of the alkene. A mecha
Elimination and Addition Reactions. Part 41. Nucleophilic Eliminative Fission of Cyclopropanes: the Coiled Spring Effect of Ring Strain on Nucleofugality and its Evaluation
Hughes, Simon,Griffiths, Gwerydd,Stirling, Charles J. M.
, p. 1253 - 1264 (2007/10/02)
Rates have been measured of sulphonyl-activated eliminative ring fissions of a series of six cyclopropanes in which the leaving group is stabilised by alkoxycarbonyl, cyano, or sulphonyl groups.The measurements allow assignment of ranks (nucleofugalities) to carbon leaving groups in systems in which the connection to the leaving group is strained by incorporation in a cyclopropane ring.The values obtained are compered with those obtained for a unstrained (acyclic) analogues.Rank enhancements of about 9(log) units are obtained; these enhancements suggests that free energies of activation for leaving-group expulsion are reduced by about 53 kJmol-1, or about 46 percent of these excess of enthalpy of the strained ring, notwithstanding the small degree of ring fission in the transition structure.The effect of phenyl substitution at the leaving group suggests that cleavage of the ring is very little advanced in the transition structure, although this is variable with the nature of the leaving-group stabilisation.This is the first direct determination of the effect of strain on nucleofugality.
