Abstract
The molecular orbital (MO) calculations predict that the the reaction of the mesylate ( 2) of tropone oxime with nucleophiles will lead to the ring opening of the substrate. In accord with this MO prediction we have found experimentally that the facile ring opening of 2 occurs while the oxime 3 is inert to nucleophiles. Thus, 2 reacts with nucleophiles under mild conditions and gives stereoselectively a variety of (Z,Z,Z)-trienes, as the sole products in high yields. The reaction is similar to that of the tosylate 1. The reaction has been found to be caused by the intramolecular ( HOMO → σ ∗ ) charge transfer in the Meisenheimer tetrahedral intermediate. A hyperconjugation plus E2 mechanism is proposed for the facile ring opening. The MO theory interprets why the troponoid rings of the mesylate and tosylate are cleaved easily by nucleophiles.
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