title: Corrole and nucleophilic aromatic substitution are not incompatible: a novel route to 2,3-difunctionalized copper corrolates.
abstract: The insertion of a -NO2 group onto the corrole framework represents a key step for subsequent synthetic manipulation of the macrocycle based on the chemical versatility of such a functionality. Here we report results of the investigation of a copper 3-NO2-triarylcorrolate in nucleophilic aromatic substitution reactions with "active" methylene carbanions, namely diethyl malonate and diethyl 2-chloromalonate. Although similar reactions on nitroporphyrins afford chlorin derivatives, nucleophilic attack on carbon-2 of corrole produces 2,3-difunctionalized Cu corrolates in acceptable yields (ca. 30%), evidencing once again the erratic chemistry of this contracted porphyrinoid.
authors.affiliation: Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma Tor Vergata, 00133 Roma, Italy. manuela.stefanelli@uniroma2.it.
authors.forename: M
authors.initials: M
authors.lastname: Stefanelli
authors.forename: F
authors.initials: F
authors.lastname: Mandoj
authors.forename: S
authors.initials: S
authors.lastname: Nardis
authors.forename: M
authors.initials: M
authors.lastname: Raggio
authors.forename: F R
authors.initials: FR
authors.lastname: Fronczek
authors.forename: G T
authors.initials: GT
authors.lastname: McCandless
authors.forename: K M
authors.initials: KM
authors.lastname: Smith
authors.forename: R
authors.initials: R
authors.lastname: Paolesse
mesh_terms: D060326:Chemistry Techniques, Synthetic; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D009682:Magnetic Resonance Spectroscopy; D008314:Malonates / Q000737:chemistry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry; D011166:Porphyrins / Q000737:chemistry*; D011758:Pyrroles / Q000737:chemistry; D013056:Spectrophotometry, Ultraviolet
chemical_list: D008314:Malonates; D009942:Organometallic Compounds; D011166:Porphyrins; D011758:Pyrroles; C431863:corrole; C006969:chlorin; C498810:diethyl malonate; D003300:Copper