Nickel‐Catalyzed Stereospecific C−H Coupling of Benzamides with Epoxides

A Ni(OAc)2‐catalyzed C−H coupling of 8‐aminoquinoline‐derived benzamides with epoxides has been developed. The reaction proceeds with concomitant removal of the 8‐aminoquinoline auxiliary to form the corresponding 3,4‐dihydroisocoumarins directly. Additionally, the nickel catalysis is stereospecific, and the cis‐ and trans‐epoxides are converted into the corresponding cis‐ and trans‐dihydroisocoumarins with retention of configuration, which is complementary to previously reported palladium catalysis. Moreover, while still preliminary, the Csp3 −H functionalization is also achieved in the presence of modified NiCl2 catalysts. Die Konfiguration bleibt: Eine Ni(OAc)2‐katalysierte C‐H‐Kupplung von 8‐Aminochinolinbenzamiden mit Epoxiden führt direkt zur Bildung der entsprechenden 3,4‐Dihydroisocumarine; das 8‐Aminochinolin‐Auxiliar wird in der Reaktion abgespalten. Die cis‐ und trans‐Epoxide werden unter Retention der Konfiguration in die cis‐ bzw. trans‐Dihydroisocumarine umgewandelt, was komplementär zu bekannten Palladiumkatalysen ist.