Reaction of Moore's ketene ( tert-butylcyanoketene) with 1,3-cyclopentadiene and 1,3-cyclohexadiene. Is periselectivity controlled by the dynamic of trajectories at the bifurcation point?

Abstract

The cycloaddition reaction of tert-butylcyanoketene (TBCK, Moore's ketene) with 1,3-cyclopentadiene yields the [2+2] product, namely cyclobutanone 9. TBCK and 1,3-cyclohexadiene provide the cyclobutanone 10 and some of the ether 11. Both reactions yielding the cyclobutanones ( 9 and 10, respectively) are reversible. Cyclobutanone 10 is converted thermally and irreversibly into the bicyclic ether 11 via a [3,3] sigmatropic rearrangement (oxo-Cope). The X-ray single crystal data for the ether 11 confirms that the CN and the ether oxygen are in a trans configuration. Data provided by density functional calculations at B3LYP/6-311++G(d,p) level mirror the X-ray data. Furthermore, the relative thermodynamic stabilities (Δ G calculated at 273 °C, 1 atm) of the most relevant isomers of 10 at mPWB1K/6-31+G(d,p) level of theory is provided. Details of the transition states that: (i) leads to cyclobutanone 10 from TBCK and 1,3-cyclohexadiene, and (ii) the oxo-Cope rearrangement of cyclobutanone 10 to produce ether 11 are provided.