The Resurrection of Murahashi Coupling after Four Decades

Abstract

Since the discovery of the pioneering cross-coupling name reactions in the 1970s, cross-coupling involving organolithium reagents (Murahashi coupling) has been neglected for more than 30 years. It was considered to be a technically nonpractical reaction based on the poor selectivity, because of the high reactivity and low functional group tolerance of the organolithium coupling partner. In this Review, we shall provide a comprehensive update on the renaissance of Murahashi coupling that enabled chemists to overcome many difficulties by using modern catalytic systems, in conjunction with the development of appropriate reaction conditions. As the resurrection of Murahashi coupling has occurred mainly due to Feringa’s work, this transformation may be considered as Murahashi–Feringa coupling.

Emerging Trends in Cross-Coupling: Twelve-Electron-Based L1Pd(0) Catalysts, Their Mechanism of Action, and Selected Applications

“…This technology is also an example of how incremental innovation, with contributions from many pioneers, has led to a Nobel Prize. Moreover, the Murahashi reaction has recently been resurrected as the Murahashi–Feringa coupling with the significant contributions of Nobel Laureate Feringa. , The C–N cross-coupling has also become very popular and industrially relevant; hence, we are anticipating another Nobel Prize in cross-coupling in the near future. These innovations in all the areas of cross-coupling are due to the continued development of new ligands and catalysts …”

Group 16 conjugated polymers based on furan, thiophene, selenophene, and tellurophene

“…It was considered a technically nonpractical reaction due to the high reactivity, poor selectivity, and low functional group tolerance of its organolithium coupling partner. However, there has recently been a renaissance of Murahashi cross-coupling mainly due to the work of Feringa's group, 64,65 which might further revive the preparation of CPs based on this coupling. Nevertheless, there are only a handful of reports on the preparation of Group 16 conjugated polymers using Murahashi coupling.…”

Ylide-Substituted Phosphines: A Platform of Strong Donor Ligands for Gold Catalysis and Palladium-Catalyzed Coupling Reactions

“…Although the C–C coupling by Grignard reagents has been studied in great detail in combination with NHCs or phosphines with precious and even base metals, the corresponding C–C bond formation with organolithium derivatives remained for a long time far less developed . In the past decade, Feringa and co-workers established efficient protocols for the coupling of aryl/alkenyl bromides with various lithium nucleophiles even at low temperatures .…”