Abstract
Transition-metal-catalyzed cross-coupling has emerged as one of the most powerful
and useful tools for the formation of C–C and C–heteroatom bonds. Given the shortage
of resources of precious metals on Earth, the use of Earth-abundant metals as catalysts
in developing cost-effective strategies for cross-coupling is a current trend in synthetic
chemistry. Compared with the achievements made using first-row nickel, iron, cobalt,
and even manganese catalysts, the group 6 metal chromium has rarely been used to promote
cross-coupling. This perspective covers recent advances in chromium-catalyzed cross-coupling
reactions in transformations of chemically inert C(aryl)–O, C(aryl)–N, and C(aryl)–H
bonds, offering selective strategies for molecule construction. The ability of low-valent
Cr with a high-spin state to participate in two-electron oxidative addition is highlighted;
this is different from the mechanism involving single-electron transfer that is usually
assigned to chromium-mediated transformations.
1 Introduction
2 Chromium-Catalyzed Kumada Coupling of Nonactivated C(aryl)–O and C(aryl)–N Bonds
3 Chromium-Catalyzed Reductive Cross-Coupling of Two Nonactivated C(aryl)–Heteroatom
Bonds
4 Chromium-Catalyzed Functionalization of Nonactivated C(aryl)–H Bonds
5 Conclusions and Outlook
Key words
chromium catalysis - homogeneous catalysis - cross-coupling