A chemodivergent synthesis of polycyclic aromatic diarylamines and carbazoles was established by employing thermally or photochemically controlled processes using KOBu/1,10-phenanthroline. The synthetic processes involved the dephosphinylation of 9-amino-10-(phosphinyl)phenanthrenes, which were obtained through a regioselective palladium-catalyzed direct [4 + 2] benzannulation of phosphinyl ynamines with 2-iodobiphenyls. When the dephosphinylation was conducted under heating conditions (∼100 °C), it proceeded to yield 9-aminophenanthrene.
View Article and Find Full Text PDFA series of 9-amino-10-halophenanthrenes were synthesized through a one-pot process, including dephosphinylative Sonogashira-Hagihara coupling of 2-bromobiphenyls with air-stable phosphinyl ynamines, followed by halonium-promoted [4 + 2] benzannulation of the resulting 2-(aminoethynyl)biphenyls. Nonsubstituted and methyl-substituted 2-bromobiphenyls rapidly underwent the Sonogashira-Hagihara aminoethynylation and the halogenative Friedel-Crafts benzannulation to provide the corresponding amino(halo)phenanthrenes in high yields, while electron-sufficient and -deficient substrates did slowly undergo the former and the latter to result in low yields, respectively. This protocol worked well for the syntheses of highly π-extended aminophenanthrenes and aminobenzonaphthothiophenes with different optical properties.
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