Nickel-Catalyzed Dicarbofunctionalization of Alkenes

Abstract

1,2-Dicarbofunctionalization of alkenes has emerged as an efficient synthetic strategy for preparing substituted molecules by coupling readily available alkenes with electrophiles and/or nucleophiles. Nickel complexes serve as effective catalysts owing to their tendency to undergo facile oxidative addition and slow β-hydride elimination, and their capability to access both two-electron and radical pathways. Two-component alkene functionalization reactions have achieved high chemo-, regio-, and stereoselectivities by tethering one of the coupling partners to the alkene substrate. Three-component reactions, however, often incorporate directing groups to control the selectivity. Only a few examples of directing-group-free difunctionalizations of unactivated alkenes have been reported. Therefore, great opportunities exist for the development of three-component difunctionalization reactions with broad substrate scopes and tunable chemo-, regio-, and stereoselectivities.

Vitamin B12-Catalyzed Dicarbofunctionalization of Bromoalkenes Under Visible Light Irradiation

“…19 Two-component reductive dicarbofuctionalizaton of alkenes via radical cyclization is also possible with Ni catalysis. 20 In this line, we have also shown that vitamin B 12 catalysis enables dicarbofunctionalization of electron-deficient alkenes. 17 The cyclization proposed herein followed by the Giese addition would be the first example of dicarbofuntionalization of non-activated alkenes catalyzed by vitamin B 12 .…”

Nickel‐Catalyzed Regioselective Alkenylarylation of γ,δ‐Alkenyl Ketones via Carbonyl Coordination

“…Early work focused on difunctionalizing 1,1‐disubstituted terminal [7] and bicyclic [8] alkenes to avoid β‐H elimination. Recently, a broad class of substrates were functionalized using a coordination approach [1a–f] in which alkylmetal intermediates were stabilized as transient metallacycles [9] . However, this strategy requires installation and removal of strong coordinating groups like imines, [10] pyridines, [11] 2‐aminopyrimidines, [12] and 8‐aminoquinolines [13] for stabilizing metallacycles [14] .…”

Photoredox catalysis in nickel-catalyzed C–H functionalization

“…Nickel-catalyzed alkene 1,2-difunctionalization is considered as useful method for preparing complex molecules in a single-step reaction [137][138][139]. In this aspect, the groups by Kong [140] and Molander [141] independently demonstrated photoredox/nickelcatalyzed approaches to olefin difunctionalizations involving C(sp 3 )-H activation.…”