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Direct and Regioselective Amination of β‐Unsubstituted 5,15‐Diazaporphyrins with Amines: A Convenient Route to Near‐Infrared‐Responsive Diazaporphyrin Sensitizers
Author(s) -
Omomo Satoshi,
Sugai Takuma,
Minoura Mao,
Nakano Haruyuki,
Matano Yoshihiro
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201800471
Subject(s) - chemistry , amination , regioselectivity , palladium , singlet oxygen , yield (engineering) , photochemistry , infrared , singlet state , primary (astronomy) , oxygen , medicinal chemistry , organic chemistry , catalysis , excited state , materials science , physics , astronomy , nuclear physics , optics , metallurgy
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.