Synthesis of new derivatives from 1,2α,4α,5-tetramethyl-8-oxabicyclo[3.2.1]oct-6-en-3-one.

In this paper we report the synthesis of biologically active compounds through a [3+4] cycloaddition reaction to produce the main frame structure, followed by several conventional transformations. The 1,2alpha,4alpha,5-tetramethyl-8-oxabicyclo[3.2.1]oct-6-en-3-one (11) obtained from a [3+4] cycloaddition reaction was converted into 1,2alpha,4alpha,5-tetralnethyl-6,7-exo-isopropylidenedioxi-8-oxabicyclo[3.2.1]octan-3-one (13) in 46% yield. This was further converted into the alcohols 1,2alpha,4alpha,5-tetramethyl-6,7-exo-isopropylicleneclioxi-8-oxabicyclo[3.2.1]octan-3alpha-ol (14), 1,2alpha,4alpha,5-tetrainethyl-6,7-exo-isopropylidenedioxi-8-oxabicyclo[3.2.1]octan-3beta-ol (15), 1,2alpha,4alpha,5-tetratnethyl-3-butyl-6,7-exo-isopropylicleneclioxi-8-oxabicyclo[3.2.1]octan-3alpha-ol (17), 1,2alpha,4alpha,5-tetramethyl-3-hexyl-6,7-exo-isopropylidenedioxi-8-oxabicyclo[3.2.1]octan-3alpha-ol (18) and 1,2alpha,4alpha,5-tetramethyl-3-decyl-6,7-exo-isopropylidenedioxi-8-oxabicyclo[3.2.1]octan-3alpha-ol (19). Dehydration of 17, 18 and 19 with thionyl chloride in pyridine resulted in the alkenes 20, 21 and 22 in ca. 82% - 89% yields from starting alcohols. The herbicidal activity of the compounds synthesized was evaluated at a concentration of 100 mug g(-1). The most active compound was 21 causing 42,7% inhibition against Cucumis sativus L.