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PEROXIDIC INTERMEDIATES IN INDOLE–SINGLET OXYGEN REACTIONS: MECHANISM OF THE C 2 —C 3 RING CLEAVAGE OF TRYPTOPHOL *
Author(s) -
Saito Isao,
Imuta Mitsuru,
Nakada Akira,
Matsugo Seichi,
Matsuura Teruo
Publication year - 1978
Publication title -
photochemistry and photobiology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.818
H-Index - 131
eISSN - 1751-1097
pISSN - 0031-8655
DOI - 10.1111/j.1751-1097.1978.tb06964.x
Subject(s) - homolysis , chemistry , photodissociation , photochemistry , singlet oxygen , indole test , cleavage (geology) , ferrous , oxygen , ring (chemistry) , bond cleavage , redox , reaction mechanism , singlet state , medicinal chemistry , stereochemistry , radical , catalysis , excited state , organic chemistry , physics , geotechnical engineering , fracture (geology) , nuclear physics , engineering
— Photosensitized oxygenation of tryptophol (1) at –70°C gives the corresponding 3‐hydroperoxyindoline 2 as a primary product. Chemical and photochemical behaviors of the hydroperoxide (2) have been investigated. Photolysis and redox reactions of 2 with ferrous ion give a C 2 —C 3 ring cleavage product 5 together with 3‐hydroxyindoline 3. A mechanism involving O—O homolysis of the hydroperoxide has been proposed. Thermal decomposition of 2 leading to 3 and 5 is also suggested to proceed via the O—O homolysis.