Face-selective diels-alder reactions between unsymmetrical cyclohexadienes and symmetric trans-dienophile: an experimental and computational investigation
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[GRAPHICS] A combined experimental and theoretical study of the Diels-Alder reactions between 2-trimethylsiloxy-1,3-cyclohexadiene (2-11) and (E)-1,4-diphenylbut-2-ene-1,4-dione (1) is reported. Two diastercomeric products, 5-endo-6-exo- (nx) and 5-exo-6-endo- (xn) dibenzoyl derivatives, are possible with symmetric trans-dienophile (1). While in many cases 5-endo-6-exo product is preferred over the corresponding 5-exo-6-endo product, the product ratio nx:xn is found to vary with the position of substituents on the diene. The density functional theory studies with the mPWIPW91/6-31G* as well as the 133LYP/631G* levels reveal that the electrostatic repulsion between the oxygen lone pairs on the diene and the dienophile is critical to the observed product selectivities. The optimized transition state geometries though appeared to involve secondary orbital interactions, careful examination of the frontier Kohn-Sharn orbitals as well as calculations with the natural bond orbital (NBO) analyses confirm the absence of SOI in these transition states. In the case of methyl-substituted dienes, a cumulative effect of steric and electrostatic interactions between the diene and the dienophile is found to be the controlling element toward the observed selectivity.
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