69888-10-4Relevant academic research and scientific papers
Electrophilic additions to allenes. VI. The role of steric versus electronic effects in the reactions of arenesulphenyl halides with allenes
Garratt, Dennis G.,Beaulieu, Pierre L.
, p. 2738 - 2744 (2007/10/02)
The role of steric and electronic effects during the rate and product determining steps for the addition of arenesulphenyl chlorides to 1,3-disubstituted allenes has been briefly examined.Both effects appear to be generally of minimal importance during the rate determinig step.The available rate data indicate the presence of little, if any, build up of positive charge on sulphur.These results are interpreted in terms of an SN2 attack on bivalent sulphur leading to an alkylidenethiiranium ion intermediate.Steric effects are of greater importance in the product determinig step, particularly when the sulphenyl chlorides possess two bulky ortho substituents, as in the case of 2,4,6-triisopropylbenzenesulphenyl chloride.
