Facile Peripheral Modification of N-Confused Porphyrin

Abstract

[reaction: see text] An improved methodology for the N-alkylation of the porphyrin isomer N-confused porphyrin is presented. The combination of polar solvent conditions and the use of the base Cs2CO3 affords externally modified products in high yield without separation difficulties and without the use of large excesses of alkylating reagent. The further transformation and metalation of these products provides opportunities for the construction of metalloenzyme model complexes, peptide adducts, and chromophore assemblies.

N-Confused Porphyrin Immobilized on Solid Supports: Synthesis and Metal Ions Sensing Efficacy

“…5,10,15,20-tetraphenyl-2-aza-21-carbaporphyrin (NCTPP) and 2- N -propyl-5,10,15,20-tetraphenyl-2-aza-21-carbaporpyrin (NCTPP-Pr + ) were prepared according with literature procedures. The characterization of NCTPP and NCTPP-Pr + were performed by 1 H-NMR, UV-Vis and mass spectrometry with all the experimental data being in agreement with the described literature data [ 59 , 65 ].…”

“…In this study, in order to avoid the formation of a sandwich type complex, thereby assuring a similar geometry in immobilized NCTPP and non-immobilized NCTPP and to ensure that the inner core nitrogens are the unique site able to interact with heavy metal cations, the alkylation of NCTPP was performed using propyl iodide, according to a literature procedure, affording the expected NCTPP-Pr + ( Figure 1 ) [ 65 ].…”

The metal complexes of N-confused porphyrin as heme model compounds

“…While the alkylation of NCP has been known since the discovery of the macrocycle, efficient conditions for functionalization of this position with a variety of both active and inactive alkylating reagents remained elusive [51][52][53]. We recently presented a report on universal conditions for the alkylation of free base NCP [54]. By using a small percentage of a polar solvent in a non-polar medium along with the non-coordinating base Cs 2 (CO 3 ), we can efficiently alkylate the external nitrogen with a variety of groups with yields up to 95% (Figs.…”

“…However, with successful activation of the internal C-H bond, heme-like structures can be generated, which bodes well for future work with this macrocycle. [54]. …”

The first manganese N-confused porphyrins catalyzed oxidation of alkene

“…The presence of an external nitrogen may impart some peculiar characteristics to N-confused porphyrin. For example, it may involve in the electrophilic reaction and results in the formation of the alkylation products [9,10]. Unlike N-confused porphyrin, it's alkylation products do not undergo NH-tautomerism and have only one stable form, which can form manganese(III) N-confused porphyrin having a direct carbon-manganese (Mn-C) bond [11].…”