Reactions of 2,3,5-trichloro-4,4-ethylenedioxy-2-cyclopentenone with some ambident nucleophiles. Sterically loaded functionalized 6-azabicyclo[3.1.0]hex-5-enes

2,3,5-Trichloro-4,4-ethylenedioxy-2-cyclopentenone reacted with sodium azide in tetrahydrofuran to give the expected 3-azido derivative which was converted into 1,3-dichloro-4,4-ethylenedioxy-6-azabicyclo-[3.1.0]hex-5-en-2-one and 3-amino-2,5-dichloro-4,4-ethylenedioxy-2-cyclopentenone on heating in chloroform. The reaction of 2,3,5-trichloro-4,4-ethylenedioxy-2-cyclopentenone with potassium thiocyanate, depending on the conditions, afforded the corresponding 3-thiocyanato derivative or symmetric sulfide. Treatment of the title compound with hydroxylamine resulted in opening of the dioxolane ring with simultaneous formation of oxime via replacement of chlorine at the neighboring sp²-carbon atom.Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 10, 2004, pp. 1569–1573.Original Russian Text Copyright © 2004 by Shavaleeva, Ivanova, Usmanova, Akhmetvaleev, Miftakhov.