Photochemical generation of six- and five-membered cyclic vinyl cations.
The photochemical solvolyses of 4-tert-butylcyclohex-1-enyl(phenyl)iodonium tetrafluoroborate (1) and cyclopent-1-enyl(phenyl)iodonium tetrafluoroborate (2) in methanol yield vinylic ethers and vinylic cycloalkenyliodobenzenes and cycloalkenylbenzene, which are the trapping products of the geometrically destabilized C6-ring and C5-ring vinyl cation with the solvent and with the leaving group iodobenzene. Iodonium salt 2 also yields an allylic ether and allylic cyclopentenyliodobenzenes and cyclopentenylbenzene, which are the trapping products of the C5-ring allylic cation produced from the C5-ring vinyl cation by a hydride shift in a typical carbocationic rearrangement.
Slegt
Micha
M
Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
Gronheid
Roel
R
van der Vlugt
Dennis
D
Ochiai
Masahito
M
Okuyama
Tadashi
T
Zuilhof
Han
H
Overkleeft
Hermen S
HS
Lodder
Gerrit
G
D002412:Cations / Q000138:chemical synthesis / Q000737:chemistry / Q000528:radiation effects; D003516:Cycloparaffins / Q000138:chemical synthesis* / Q000737:chemistry / Q000528:radiation effects*; D008958:Models, Molecular; D015394:Molecular Structure; D010777:Photochemistry; D013237:Stereoisomerism; D014466:Ultraviolet Rays; D014753:Vinyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry / Q000528:radiation effects*
D002412:Cations; D003516:Cycloparaffins; D014753:Vinyl Compounds