Department of Fundamental Sciences, Graduate School of Science and Technology, Niigata University, Nishi-ku, Niigata, 950-2181, Japan.
Department of Chemistry, College of Science, Rikkyo University, Toshima-ku, Tokyo, 171-8501, Japan.
Angew Chem Int Ed Engl. 2018 Mar 26;57(14):3797-3800. doi: 10.1002/anie.201800471. Epub 2018 Mar 1.
We have established a convenient method for the base-promoted direct amination of β-unsubstituted 5,15-diazaporphyrins (DAPs) with secondary and primary amines to produce 3,7,13,17-tetraamino- and 3-amino-DAPs, respectively, regioselectively. The amino groups attached at the periphery cause significant red shifts of the absorption bands as a result of their perturbation of the HOMO and/or LUMO in the DAP π-system. The palladium complex of a 3,7,13,17-tetrakis(diphenylamino)-DAP generated singlet oxygen in high yield under irradiation with near-infrared light.
我们建立了一种方便的方法，用于在碱促进下，β-未取代的 5,15-二氮杂卟啉（DAPs）与仲胺和伯胺进行直接胺化，分别得到 3,7,13,17-四氨基-DAP 和 3-氨基-DAP，具有区域选择性。外围连接的氨基基团由于它们对 DAP π 体系中的 HOMO 和/或 LUMO 的干扰，导致吸收带发生显著的红移。在近红外光照射下，3,7,13,17-四（二苯基氨基）-DAP 的钯配合物可以高产率地生成单线态氧。
