Effect of Ring Size and Migratory Groups on [1,n] Suprafacial Shift Reactions. Confirmation of Aromatic and Antiaromatic Transition-State Character by Ring-Current Analysis.
Suprafacial sigmatropic shift reactions of 5-substituted cyclopentadienes, 3-substituted cyclopropenes, and 7-substituted cycloheptatrienes have been studied computationally at the MP2/6-31+G* level for structures and energetics and with the ipsocentric method at the CHF/6-31G** level to calculate current-density maps. The hydrogen shifts in cyclopentadienes have a diatropic ring current indicating aromatic, cyclopentadienide anion character. This result stands in contrast to the fluorine shift in 5-fluorocyclopentadiene which requires much more energy and has a paratropic ring current in the TS pointing to antiaromatic, cyclopentadienyl cation character. [1,3] hydrogen shifts in cyclopropenes are very difficult, passing through transition states that have an extended C-C bond. For 3-fluorocyclopropene, the [1,3] fluorine shift is much easier than the hydrogen shift. For 7-fluorocycloheptatriene, the [1,7] hydrogen shift is predicted but requires very high energy and has a paratropic ring current and antiaromatic character. The [1,7] suprafacial fluorine shift is relatively easy, having a TS with cycloheptatrienyl cation character. Patterns of currents, and the reversal for H and F migration, are rationalized by orbital analysis based on the ipsocentric method. Calculated charges and structural features for reactants and transition states support these conclusions.
Department of Chemistry, University of Sheffield , Sheffield S3 7HF, U.K.
Joseph
J
Clarke
Department of Chemistry, University of Sheffield , Sheffield S3 7HF, U.K.
Patrick W
PW
Fowler
Department of Chemistry, Virginia Commonwealth University , 1001 West Main Street, Richmond, Virginia 23284, United States.
Scott
S
Gronert
Department of Chemistry and Biochemistry, San Francisco State University , 1600 Holloway Avenue, San Francisco, California 94132, United States.
James R
JR
Keeffe