E,E- and E,Z-α-phenyl-α′-acetoxyorthoquinodimethane: steric and electronic control of cycloaddition reactions

Abstract
E,E- and E,Z-α-phenyl-α′-acetoxyorthoquinodimethanes have been prepared from the corresponding cis- and trans-1-acetoxy-3-phenyl-1,3-dihydrobenzo[c]thiophene-2,2-dioxides. The regio- and diastereoselectivity of the addition reactions with dimethyl fumarate, dimethyl maleate, maleic anhydride, and methyl crotonate have been determined. Abinitio calculations have been carried out on orthoquinodimethane and its α-phenyl and α-oxy derivatives. A correlation has been made between the steric and electronic properties of the orthoquinodimethanes and the regio- and diastereoselectivity of their Diels–Alder reactions.

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