School of Chemistry, University of East Anglia, Norwich Research Park, Norwich, NR4 7TJ, UK.
UK National Crystallography Service, Chemistry University of Southampton, Southampton, SO17 1BJ, UK.
Angew Chem Int Ed Engl. 2021 Mar 29;60(14):7632-7636. doi: 10.1002/anie.202016596. Epub 2021 Mar 1.
Phthalocyanines and porphyrins are often the scaffolds of choice for use in widespread applications. Synthetic advances allow bespoke derivatives to be made, tailoring their properties. The selective synthesis of unsymmetrical systems, particularly phthalocyanines, has remained a significant unmet challenge. Porphyrin-phthalocyanine hybrids offer the potential to combine the favorable features of both parent structures, but again synthetic strategies are poorly developed. Here we demonstrate strategies that give straightforward, controlled access to differentially substituted meso-aryl-tetrabenzotriazaporphyrins by reaction between an aryl-aminoisoindolene (A) initiator and a complementary phthalonitrile (B). The choice of precursors and reaction conditions allows selective preparation of 1:3 Ar-ABBB and, uniquely, 2:2 Ar-ABBA functionalized hybrids.
酞菁和卟啉通常是广泛应用中首选的支架。合成方面的进展允许定制衍生物，从而调整其性质。非对称体系，特别是酞菁的选择性合成仍然是一个重大的未满足的挑战。卟啉-酞菁杂化物具有结合双亲结构优势的潜力，但合成策略仍未得到充分发展。在这里，我们展示了通过芳基-氨基异吲哚啉（A）引发剂与互补的酞腈（B）之间的反应，可直接、可控地获得不同取代的间-芳基-四苯并三氮唑卟啉的策略。通过选择前体和反应条件，可以有选择性地制备 1:3 Ar-ABBB，并且独特地制备 2:2 Ar-ABBA 官能化的杂化物。
