Rationalisation of patterns of competing reactivity by X-ray structure determination : reaction of isomeric (benzyloxythienyl)oxazolines with a base

Abstract

Three isomeric (benzyloxythienyl)oxazolines 9 , 11 and 13 have been prepared and are found, upon treatment with strong base, to undergo either Wittig rearrangement or intramolecular attack of the benzylic anion on the oxazoline function to give products derived from cleavage of the initially formed 3-aminothienofuran products. This pattern of reactivity is directly linked to the distance between the two reactive groups as determined by X-ray diffraction, with the greatest distance in 11 leading to exclusive Wittig rearrangement, the shortest distance in 13 giving exclusively cyclisation-derived products, and the intermediate distance in 9 leading to both processes being observed. The corresponding N-butyl amides were also obtained in two cases and one of these undergoes efficient Wittig rearrangement leading to a thieno[2,3-c]pyrrolone product.