Formate‐Mediated Cross‐Electrophile Reductive Coupling of Aryl Iodides and Bromopyridines

Abstract

Two catalytic systems for the formate-mediated cross-electrophile reductive coupling of aryl iodides with 6bromopyridines are described. Using homogenous rhodium or heterogeneous palladium catalysts, the products of reductive biaryl cross-coupling could be formed in moderate yield with excellent levels of chemoselectivity.

Nickel-Catalyzed Cross-Electrophile Coupling between C(sp2)–F and C(sp2)–Cl Bonds by the Reaction of ortho-Fluoro-Aromatic Amides with Aryl Chlorides

“…Thus, both electrophiles can compete for oxidative addition to the catalyst. To achieve selective cross-electrophile coupling and to avoid the formation of homocoupling products, the use of two electrophiles that have electronically and/or sterically different reactivities, the use of an excess amount of a less reactive coupling partner, or utilizing different activation modes for each electrophile are typically employed . In 2015, Weix reported a new strategy using a Ni/Pd dual catalytic system for cross-electrophile coupling between aryl bromides and aryl triflates.…”

From Hydrogenation to Transfer Hydrogenation to Hydrogen Auto-Transfer in Enantioselective Metal-Catalyzed Carbonyl Reductive Coupling: Past, Present, and Future

“…Beyond the transformations discussed in this Perspective, there exist numerous other classical carbanionic and metal-mediated processes that could potentially be accomplished via hydrogenation, transfer hydrogenation, or hydrogen autotransfer, potentially availing more scalable, sustainable, and cost-effective methods for chemical manufacture . Indeed, progress toward transfer hydrogenative pinacol reactions and cross-electrophile reductive couplings has been described. Recent advances in catalytic asymmetric photoreduction might offer new approaches to the development of more benign reductive C–C coupling protocols .…”

Mechanistic views and computational studies on transition-metal-catalyzed reductive coupling reactions

“…73 Weix and co-workers published a Ni/Pd-catalyzed reductive C(sp 2 )-C(sp 2 ) coupling between aryl bromides and aryl triflates (Scheme 2(d)). 74 Recently, the insertive reductive coupling reactions [75][76][77][78][79][80][81][82] introducing intercalating reagents (olefins, alkynes, carbine, etc.) have attracted wide attention and have been widely applied due to their ability to simplify the assembly of complex structures by constructing multiple C-C bonds with excellent chemoselectivity and syn/anti-selectivity.…”

“…Recently, the insertive reductive coupling reactions 75–82 introducing intercalating reagents (olefins, alkynes, carbine, etc. ) have attracted wide attention and have been widely applied due to their ability to simplify the assembly of complex structures by constructing multiple C–C bonds with excellent chemoselectivity and syn / anti -selectivity.…”