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 a 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.

Keywords

• oxazoline
• Wittig rearrangement
• thiophene
• thieno[2,3-<i>c</i>]pyrrolone
• X-ray structure