Rhenium(I)‐Catalyzed ortho‐C−H Addition to Bicyclic Alkenes

Abstract

Hydroarylation of bicyclic alkenes has been developed using a low-valent Re -catalyzed, directing group-assisted C-H bond activation strategy. The addition of sodium acetate significantly improves the reaction efficiency; moreover, bicyclic alkenes such as 7-oxa and aza benzonorbornadienes worked efficiently under this reaction condition. Preliminary mechanistic studies suggest that, after the alkene insertion, the rhenacycle preferentially undergoes protonolysis rather than reductive elimination.

A DFT Study on the Mechanism and Origin of Regioselectivity in the Rhodium/Diene‐Catalyzed Ring‐Opening Reactions of C1‐Substituted Oxabenzonorbornadienes with Arylboronic Acids

“…Transition‐metal‐catalyzed reactions of oxabicyclic derivatives have been an intense area of research in the last 20 years [1a–c] . Over the years, many interesting transformations have been investigated such as cycloadditions, [2a–f] isomerizations, [3a–e] dimerizations, [4a–c] among other reactions that have been reported [5a–c] . Of particular interest are nucleophilic ring‐opening reactions of oxabicyclic alkenes, as they provide access to a broad family of synthetic building blocks bearing multiple stereocenters in a single step [6] with many of these functionalized intermediates useful in natural product synthesis and as motifs in medicinal chemistry [7a,b] .…”

Rhenium-catalysed reactions in chemical synthesis: selected case studies

“…2). 82 Pyrimidines have been used to direct the selective 2-alkenylation of indoles with alkenes ( product 11g). 83 N-Carbamoylindoles delivered pyrroloindolones 11h in reactions with internal alkynes.…”

Transition metal-catalyzed coupling of heterocyclic alkenesviaC–H functionalization: recent trends and applications

“…Later, the hydroarylation of arenes with heterobicyclic alkenes by Re-catalysis was found to be successful (Scheme 69). 105 The reaction proceeds at high temperature (130°C) in the presence of NaOAc. A wide range of arenes, heterobicyclic alkenes and heterocyclic azoles work effectively to generate the exo-products.…”