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Current Organic Synthesis


ISSN (Print): 1570-1794
ISSN (Online): 1875-6271

Review Article

Recent Advances in Transition Metal-Catalyzed Reactions of Oxabenzonorbornadiene

Author(s): Rebecca Boutin, Samuel Koh and William Tam*

Volume 16, Issue 4, 2019

Page: [460 - 484] Pages: 25

DOI: 10.2174/1570179416666181122094643


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.

Keywords: Oxabenzonorbornadiene, cyclopropanated oxabenzonorbornadiene, transition metal catalysis, ring-opening, asymmetric ringopening, cycloaddition.

Graphical Abstract
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