Recent Advances in Nickel-Catalyzed Three-Component Difunctionalization of Unactivated Alkenes

Abstract

Catalytic, intermolecular difunctionalization of alkenes represents an efficient and diverse protocol for the buildup of molecular complexity from abundant materials by forging two chemical bonds in a single operation. Despite important progress in this area, transition-metal-catalyzed three-component difunctionalization of unactivated alkenes remains underdeveloped, mainly because of the low reactivity, reduced polarization, and high tendency toward β-hydride elimination of these compounds. In this context, nickel-catalyzed, selective, intermolecular difunctionalization methods that generally proceed via two distinct reaction pathways, migratory insertion of nickel species into alkenes and radical addition to alkenes, have been developed. This short review highlights recent advances in this area.1 Introduction2 Nickel-Catalyzed Three-Component Difunctionalization of Unactivated­ Alkenes via Migratory Insertion Processes3 Nickel-Catalyzed Three-Component Difunctionalization of Unactivated­ Alkenes via Radical Processes4 Conclusions and Perspectives

General Method for Selective Three-Component Carboacylation of Alkenes via Visible-Light Dual Photoredox/Nickel Catalysis

“…During the last several years, synergistic nickel catalysis with visible-light photoredox catalysis, furnishing an emerging activation tool for the generation of highly active open-shell radical species under mild conditions, has emerged as an efficient and appealing method for the achievement of selective dicarbofunctionalization of alkenes . Sequential introduction of two functional groups in one step and upgrading the complexity of the molecules from simple raw materials can also be achieved by this synergistic strategy, which has been pioneered by the groups of Campbell, García-Domínguez, Sun, Guo, and Xu and extensively exploited by themselves and others.…”

Metal-free visible-light-enabled vicinal trifluoromethyl dithiolation of unactivated alkenes

“…The vicinal difunctionalization of olefins to introduce two functional groups across a double bond has appeared as a powerful transformation to rapidly increase molecular complexity in synthetic chemistry with improved efficiency [18][19][20][21][22]. Various transition-metal-mediated approaches for the trifluoromethylthio (SCF 3 ) difunctionalization of alkenes, such as cyanation [23], etherification [24][25][26][27], amination [28][29][30], chlorination [31,32], hydrogenation [33], trifluoromethylation [34], phos-Scheme 1: Origin of the reaction design.…”

Metal-free visible-light-enabled vicinal trifluoromethyl dithiolation of unactivated alkenes

“…[11][12][13][14][15][16][17] The vicinal difunctionalization of olefins to introduce two functional groups across a double bond has appeared as a vigorous transformation to rapidly increase molecular complexity in synthetic chemistry with improved efficiency. [18][19][20][21][22] Various transition-metal mediated approaches for trifluoromethylthio (SCF3)…”