Oxidative Coupling of an Enaminoporphyrin: C−C, N−N Linkages or Both?. Issue 11 (10th September 2015)

• Record Type: Journal Article
• Authors: Jimenez, Angel J.; Mesa, Noelia Sabater; Pereira, Ana Mafalda V. M.; Jean, Marion; Vincent, Bruno; Jeandon, Christophe; Gisselbrecht, Jean‐Paul; Ruppert, Romain
• Is Part Of: Asian journal of organic chemistry. Volume 4:Issue 11(2015:Nov.)
• Page Start: 1294
• Page End: 1300
• Publication Date: 2015-09-10
• Subjects: atropisomerism -- axial chirality -- nitrogen ligands -- oxidative coupling -- porphyrinoids; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; 547.005
• DOI: 10.1002/ajoc.201500279
• Languages: English
• ISSNs: 2193-5807

Abstract

Abstract: A symmetrical bis‐nickelporphyrin was prepared in very good yield by oxidative coupling of a nickel(II) enaminoporphyrin. This dimer was obtained by the intermolecular reaction of the starting enamine (acting as nucleophile) with the porphyrin radical cation (acting as electrophile) generated in situ. Alternatively, by using different reaction conditions, an N−N linked porphyrin dimer was obtained in moderate yield. The monomeric extended porphyrin leading to the N−N linked dimer was obtained by the intramolecular reaction of the same radical cation with the neighbouring meso ‐aryl group (acting as nucleophile). Abstract : Di‐versity : The porphyrin dimer shown was obtained in very good yields by oxidative coupling of a monomeric nickel(II) enaminoporphyrin. The enantiomers were separated by analytical chiral HPLC. Under high dilution conditions, a different dimer was isolated.