Stereoselective tandem iridium-catalyzed alkene isomerization-cope rearrangement of ω-diene epoxides: efficient access to acyclic 1,6-dicarbonyl compounds

The Cope rearrangement of 2,3-divinyloxiranes, a rare example of epoxide C-C bond cleavage, results in 4,5-dihydrooxepines which are amenable to hydrolysis, furnishing 1,6-dicarbonyl compounds containing two contiguous stereocenters at the 3- and 4-positions. We employ an Ir-based alkene isomerization catalyst to form the reactive 2,3-divinyloxirane in situ with complete regio- and stereocontrol, which translates into excellent control over the stereochemistry of the resulting oxepines and ultimately to an attractive strategy towards 1,6-dicarbonyl compounds.

Automated summary

The Cope rearrangement of 2,3-divinyloxiranes leads to the formation of 4,5-dihydrooxepines with two contiguous stereocenters, allowing for efficient synthesis of 1,6-dicarbonyl compounds through hydrolysis. Using an Ir-based catalyst enables excellent control over regio- and stereochemistry, providing a promising strategy for the synthesis of these compounds.