A ligand and Palladium‐free Avenue for Cyanation of Aryl Halides: The Art of Samarium Powder in C–C Coupling Reaction

Abstract

This is the first study of samarium powder catalyzed cyanation reaction of aryl halides, bearing electron‐withdrawing and electron‐releasing substituents, in the presence of NaCN to afford corresponding benzonitriles in high yields. This protocol takes the advantage of being done in the absence of additive, ligand and precious transition metals such as palladium.

Organic Synthesis with Elemental Lanthanides – Going Beyond Samarium and Ytterbium

“…[36] Very recently, the cyanation of aryl halides under samarium catalysis was reported (Scheme 17b). [37] Good substrate scope was observed for aryl iodides and bromides 76. A possible radical mechanism was proposed for the formation of 79.…”

“…Sm metal catalyzed (a) Sonogashira coupling and (b) cyanation of arylhalides. [36,37] reactions. Due to their lower reactivity towards oxygen, they can be considered as a safer alternative to alkali metals.…”

“…In 2009, it was shown that Sm metal catalyzed the Sonogashira coupling of aryl iodides 76 and alkynes 77 (Scheme 17a) [36] . Very recently, the cyanation of aryl halides under samarium catalysis was reported (Scheme 17b) [37] . Good substrate scope was observed for aryl iodides and bromides 76 .…”

Synthesis and characterization of a green and recyclable arginine-based palladium/CoFe2O4 nanomagnetic catalyst for efficient cyanation of aryl halides

“…19 Recently, the exploration of transition metal-catalyzed cyanation reactions involving aryl halides, utilizing metals such as Ni, 20 Cu, 21 and Pd, 22 has attracted considerable attention. Additionally, a range of protocols employing different cyano sources like NaCN, 23 KCN, 24 TMSCN, 22 Zn(CN) 2 (ref. 25), and CuCN 26 have been reported for transition metal-catalyzed cyanation reactions.…”