Direct and Regioselective Amination of β‐Unsubstituted 5, 15‐Diazaporphyrins with Amines: A Convenient Route to Near‐Infrared‐Responsive Diazaporphyrin Sensitizers. Issue 14 (1st March 2018)

• Record Type: Journal Article
• Authors: Omomo, Satoshi; Sugai, Takuma; Minoura, Mao; Nakano, Haruyuki; Matano, Yoshihiro
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 14(2018)
• Page Start: 3797
• Page End: 3800
• Publication Date: 2018-03-01
• Subjects: amination -- C−H activation -- diazaporphyrins -- dyes/pigments -- porphyrinoids; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201800471
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: 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. Abstract : At a single stroke : A convenient method has been developed for the base‐promoted direct amination of β‐unsubstituted 5, 15‐diazaporphyrins (DAP) with secondary and primary amines to produce 3, 7, 13, 17‐tetraamino‐ and 3‐amino‐DAPs, respectively (see scheme; Ar=2, 4, 6‐Me3 C6 H2 ). The palladium complex of the 3, 7, 13, 17‐tetrakis(diphenylamino)‐DAP generated singlet oxygen in high yield under irradiation with near‐infrared light.