Rebecca Boutin, Samuel Koh and William Tam* Pages 460 - 484 ( 25 )
Background: Oxabenzonorbornadiene (OBD) is a useful synthetic intermediate capable of undergoing multiple types of transformations due to three key structural features: a free alkene, a bridged oxygen atom, and a highly strained ring system. Most notably, ring-opening reactions of OBD using transition metal catalysts and nucleophiles produce multiple stereocenters in a single step. The resulting dihydronaphthalene framework is found in many natural products, which have been shown to be biologically active.
Objective: This review will provide an overview of transition metal-catalyzed reactions from the past couple of years including cobalt, copper, iridium, nickel, palladium and rhodium- catalyzed reactions. In addition, the recent derivatization of OBD to cyclopropanated oxabenzonorbornadiene and its reactivity will be discussed.
Conclusion: It can be seen from the review, that the work done on this topic has employed the use of many different transition metal catalysts, with many different nucleophiles, to perform various transformations on the OBD molecule. Additionally, depending on the catalyst and ligand used, the stereo and regioselectivity of the product can be controlled, with proposed mechanisms to support the understanding of such reactions. The use of palladium has also generated a cyclopropanated OBD, with reactivity similar to that of OBD. An additional reactive site exists at the distal cyclopropane carbon, giving rise to three types of ring-opened products.
Oxabenzonorbornadiene, cyclopropanated oxabenzonorbornadiene, transition metal catalysis, ring-opening, asymmetric ringopening, cycloaddition.
Department of Chemistry, University of Guelph, Guelph, Ontario N1E 2W1, Department of Chemistry, University of Guelph, Guelph, Ontario N1E 2W1, Department of Chemistry, University of Guelph, Guelph, Ontario N1E 2W1