Reaction of Chlorosulfonyl Isocyanate with Fluorosubstituted Alkenes: Evidence of a Concerted Pathway

• Published in: Journal of organic chemistry Vol. 75; no. 22; pp. 7913 - 7916
• Main Authors: Shellhamer, Dale F, Davenport, Kevyn J, Hassler, Danielle M, Hickle, Kelli R, Thorpe, Jacob J, Vandenbroek, David J, Heasley, Victor L, Boatz, Jerry A, Reingold, Arnold L, Moore, Curtis E
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 19.11.2010; Amer Chemical Soc
• Subjects: Chemical reactivity; Chemistry; Chemistry, Organic; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with only one n hetero atom and condensed derivatives; Organic chemistry; Physical Sciences; Preparations and properties; Reactivity and mechanisms; Science & Technology; INTRINSIC REACTION COORDINATE; PERTURBATION-THEORY; CHEMISTRY; OLEFINS; SYSTEMS; MODEL; ENERGIES; SOLVATION; BETA-LACTAMS; MOLECULES; Organic isocyanate; Quantum chemistry; Sulfone; Fluorine; Nitrogen heterocycle; Electrophilic addition; Theoretical study; Stepwise mechanism; Lactone; Reaction coordinate; Pyrimidine base; Alkene; Vinylic compound; Transition state; Stereospecificity; Concerted reaction; Chemical reactivity; Uracil; Ethylenic compound
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo101240s

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.