Reaction of chlorosulfonyl isocyanate with fluorosubstituted alkenes: evidence of a concerted pathway.
Concerted reactions are indicated for the electrophilic addition of chlorosulfonyl isocyanate with monofluoroalkenes. A vinyl fluorine atom on an alkene raises the energy of a stepwise transition state more than the energy of the competing concerted pathway. This energy shift induces CSI to react with monofluoroalkenes by a one-step process. The low reactivity of CSI with monofluoroalkenes, stereospecific reactions, the absence of 2:1 uracil products with neat fluoroalkenes, and quantum chemical calculations support a concerted pathway.
Shellhamer
Dale F
DF
Department of Chemistry, Point Loma Nazarene University, San Diego, California 92106-2899, United States.
Davenport
Kevyn J
KJ
Hassler
Danielle M
DM
Hickle
Kelli R
KR
Thorpe
Jacob J
JJ
Vandenbroek
David J
DJ
Heasley
Victor L
VL
Boatz
Jerry A
JA
Reingold
Arnold L
AL
Moore
Curtis E
CE