Progress in Transition Metal-Catalyzed Asymmetric Ring-Opening Reactions of Azabicyclic Alkenes

Abstract

The recent progress in transition metal-catalyzed ring-opening reactions of azabicyclic alkenes was reviewed focused on the influence of the types of transition metal catalysts, nucleophiles, ligands, the structures of azabicyclic alkenes and its derivatives, solvents and additives on the ring-opening reactions. Moreover, the possible mechanisms of the ring-opening reactions were also discussed.

Iridium/Copper Co-catalyzed Anti-Stereoselective Ring Opening of Oxabenzonorbornadienes with Grignard Reagents

“…Development of new methods and efficient strategies for carbon–carbon bond-forming processes that can create multiple stereocenters is one of the challenges in synthetic organic chemistry. The transition-metal-catalyzed ring-opening reaction of oxa- and azabicyclic alkenes have provided an important method to construct C–C and C–X bond formation . This process may afford valuable hydronaphthalene scaffolds of a wide range of natural products and bioactive molecules .…”

Palladium/Lewis Acid Co-catalyzed Divergent Asymmetric Ring-Opening Reactions of Azabenzonorbornadienes with Alcohols

“…The asymmetric ring-opening (ARO) reactions of oxa/azabenzonorbornadienes can directly generate substituted chiral dihydronaphthalenes, which are ubiquitous substructures in natural products and pharmaceuticals, as products . Pioneered by Lautens, the ARO reactions of oxabenzonorbornadienes have been greatly developed in the past decades, and various nucleophiles have been successfully applied as effective ring-opening reagents .…”

Iridium-Catalyzed Asymmetric Addition of Thiophenols to Oxabenzonorbornadienes

“…Heterobicyclic alkenes are versatile building blocks for the synthesis of stereochemically defined complex molecules . Considerable progress has been made in transition-metal-catalyzed asymmetric ring opening (ARO) reactions since Lautens’s seminal work.…”