Stereocontrolled Synthesis of Cyclic Ethers by Intramolecular Hetero-Michael Addition. 6. A Computational Study of the Annelation to 2,3-Disubstituted Tetrahydropyrans

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Abstract

A computational study at the ab initio level of the cyclization of (E)- and (Z)-7-hydroxy-4-substituted-2,3-unsaturated esters leading to 2,3-disubstituted tetrahydropyrans has been performed. The study showed the requirement of coordination between the pre-tetrahydropyranyl oxygen and that of the carbonyl of the α,β-unsaturated ester with the cation of the base used to obtain a suitable transition state model. The calculations using the 6-31G*//3-21G basis set show different relative stabilities for the final products and transition states leading to them. The 6-31+G* basis set was used as a calibration of the less energetic transition states. A model assuming a pre-chair conformation locating the chiral inductor equatorial and approaching the α,β-unsaturated ester in axial mode for the E isomer and equatorial for the Z geometry rationalizes the experimental results. The scope and limitations of the model applied to 2,3,5,6-functionalized cases are discussed.

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