Iron(II) Phthalocyanine-Catalyzed Homodimerization and Tandem Diamination of Diazo Compounds with Primary Amines: Access to Construct Substituted 2,3-Diaminosuccinonitriles in One-Pot

Abstract

We herein first report the homodimerization and tandem diamination of diazo compounds with primary amines catalyzed by the iron(II) phthalocyanine (PcFe(II)), which can construct one C−C bond and two C−N bonds within 20 min in one-pot. Compared to the traditional metal-catalyzed N−H insertion reaction between amines with diazo reagents, the developed reaction almost does not generate the N−H insertion product, but the homodimerization/tandem diamination product. The proposed mechanism studies indicate that primary amines play a crucial role in the homocoupling of diazo compounds via dimerization of iron(III)−acetonitrile radical generated from the reaction between diazoacetonitrile with PcFe(II) coordinated by bis(amines); the β-hydride elimination is involved, and then, the attack of primary amines toward the carbon atoms on the formed C−C bond is followed. Moreover, this novel reaction can be used to effectively prepare substituted 2,3-diaminosuccinonitriles with high yields and even up to >99:1 d.r., encouragingly these products contain both 1,2-diamines and succinonitrile motifs, which are two classes of important organic compounds with significant applications in many yields. This reaction is also suitable for the gramscale preparation of 2,3-bis(phenylamino)succinonitrile (2a) with a yield of 84%. Therefore, the developed reaction represents a new type of transformation.