The cycloaddition of heptafulvalene (1) with tetracyanoethylene (TCNE) was previously described as an example of an antarafacial cycloaddition, a [π14 a +π2 s ] process that afforded only the trans cycloadduct by virtue of the edge-to-face approach of TCNE, facilitated by the S shape of 1. The reaction has been investigated in depth and found not to be a concerted antarafacial process. At low temperature, the reaction is observed to give a mixture of cis and trans cycloadducts as well as a [4+2] cycloadduct. The mixture of products is converted to the trans cycloadduct by equilibration upon warming to room temperature. Studies with diethyl 2,3-dicyanofumarate and -maleate confirmed the formation of cis cycloadducts. DFT studies at the M06-2X/6-311+G(2d,p) SCRF=acetone level of theory show that the originally proposed edge-to-face approach of TCNE to 1 is highly disfavored, whereas a stepwise mechanism involving the addition of TCNE at C2 to form a zwitterion followed by collapse at either C2' or C7' is energetically accessible. The Diels-Alder adduct is also formed in a stepwise reaction by competitive addition of TCNE at C4 of 1. These studies suggest that edge-to-face interactions are prohibitive in even the most favorable cases.
Keywords: Woodward-Hoffmann rules; antarafacial reactions; computational chemistry; cycloaddition; heptafulvalene.
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