Aminomethylation of Oxabenzonorbornadienes via the Merger of Photoredox and Nickel Catalysis

Abstract

The first aminomethylation of oxabenzonorbornadienes using dual photoredox/nickel catalysis has been disclosed. This cascade reaction allowed the preparation of the cis-aminomethyl dihydronaphthalenols without any prefunctionalization or any use of nucleophilic organometallic species. The control of the regio-and stereoselectivity might be explained by a sequence involving insertion of nickel(0) into the C−O bond followed by the formation of a π-allyl intermediate.

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

“…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] . Such ring‐opening reactions have been carried out using a variety of carbon and heteroatom nucleophiles in the presence of Pd, [8a–f] Ni, [9a–d] Ru, [10] , Ir, [11a–c] and Rh [12a–e] complexes.…”

Organic thermally activated delayed fluorescence (TADF) compounds used in photocatalysis

“…91d) also provides a route for the formation of C(sp 3 )-C(sp 3 ) bonds via dual photoredox/Ni catalysis. 257 Operating in a similar mechanism to that illustrated in Fig. 93, the excited PC is reductively quenched by the alkylamine, furnishing an a-aminoalkyl radical after deprotonation.…”

“…91c) 256 or oxabenzonorbornadiene with alkylamines (Fig. 91d) 257 have been investigated. In the former, Ni(COD) 2 with bpy acting as the ancillary ligand, was utilised to generate the coupled poduct.…”

Nickel‐Catalyzed Allylic Substitution Reactions: An Evolving Alternative

“…The scope of the allylic substrates was later expanded to aryl-substituted allylic alcohols and carbonates, [47] while Renaud, Lautens and coworkers further extended the repertoire to α-amino radicals that upon reaction with oxabenzonorbornadienes lead to cisaminomethyl dihydronaphthalenol products. [48]…”