Synthesis of new azido porphyrins and their reactivity in copper(I)-catalyzed Huisgen 1,3-dipolar cycloaddition reaction with alkynes
摘要:
We report herein the preparation of two novel porphyrins substituted with an azido group born either on the para-position of one phenyl meso-susbtituent of a tetraaryl zinc porphyrin (1) or directly on the meso-position of a trisaryl nickel porphyrin (2). We studied the scope and the limitation the Huisgen cycloaddition reaction of these two porphyrins using different catalytic conditions. We observed that the carbene (SlMes)CuBr in THF/H2O 3:1 at 45 degrees C for 60 h gives almost quantitative yields for the reaction between I and different alkynes, but significantly lower yields with 2 probably due to its thermal instability. (c) 2007 Elsevier Ltd. All rights reserved.
Synthesis of new azido porphyrins and their reactivity in copper(I)-catalyzed Huisgen 1,3-dipolar cycloaddition reaction with alkynes
摘要:
We report herein the preparation of two novel porphyrins substituted with an azido group born either on the para-position of one phenyl meso-susbtituent of a tetraaryl zinc porphyrin (1) or directly on the meso-position of a trisaryl nickel porphyrin (2). We studied the scope and the limitation the Huisgen cycloaddition reaction of these two porphyrins using different catalytic conditions. We observed that the carbene (SlMes)CuBr in THF/H2O 3:1 at 45 degrees C for 60 h gives almost quantitative yields for the reaction between I and different alkynes, but significantly lower yields with 2 probably due to its thermal instability. (c) 2007 Elsevier Ltd. All rights reserved.
A simple and efficient method for the meso-functionalization of porphyrin has been developed. Kinetic studies of meso-fluoro-, -chloro-, -bromo-, -iodo-, and -nitro-substituted porphyrins (Ni) with phenol reveal that the reaction undergoes a typical aromatic nucleophilic substitution (SNAr) process. This catalyst-free method can be performed with meso-brominated porphyrins and oxygen-, sulfur-, and carbon-based nucleophiles to achieve a wide variety of meso-substituted porphyrins.