Oxidative Coupling <i>via</i> Organocopper Compounds

Abstract

Abstract The type of reaction described here, which achieved preparative importance before the turn of the century in the form of the Glaser reaction, has found new applications in recent years: Syntheses of 1,3‐dienes, 2,3,6,7‐tetraaza‐1,3,5,7‐tetraenes, 2,3‐diaza‐1,3‐dienes, hydrazine derivatives, bis(heteroallyl) compounds, hetarenes, polyhetarenes, cyclopolyarenes, protophanes, phanes, and heteraprotophanes. The reaction, which consists in the metalation of the starting substance followed by oxidative coupling of the metal derivative, merits special preparative interest when several successive coupling processes are possible ( e. g. polyyne, polyarene, cyclopolyarene, and protophane syntheses). The main factors limiting its applicability are the high thermal stability of some organic copper compounds and the disproportionation of the ligands that frequently occurs as a competing reaction. Selective asymmetric linkages are not generally possible by this method.