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Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions
Published on: July 17, 2020
m-Pyrenisubporphyrins and Their BIII Complexes and Reduced Congeners
1Key Laboratory of Chemical Biology and Traditional Chinese Medicine, Ministry of Educational of China, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, 410081, China.
Abstract:
m-Pyrenisubporphyrins were synthesized by Pd-catalyzed cross-coupling of α,α'-diboryl-m-pyrenitripyrrane with 9,10-bis(1,1-dibromomethylenyl)anthracene followed by oxidation with DDQ. Reaction of the m-pyrenisubporphyrin with BBr3 and triethylamine gave a B-hydroxy complex and an oxygen-atom-inserted product. Reaction of the m-pyrenisubporphyrin with PhBCl2 and triethylamine gave a B-phenyl complex. These m-pyrenisubporphyrins show red-shifted absorption bands, reflecting the incorporated pyrene segment, but are all nonaromatic. Reduction of m-pyrenisubporphyrin with p-tosylhydrazide and K2CO3 gave m-pyrenisubchlorin and m-pyrenisubbacteriochlorin, depending upon the reaction conditions. These reduced products have also been shown to be nonaromatic by the low-field shifted chemical shifts of the inner pyrrolic protons, broad and non-structured absorption bands, and small NICS values.
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