Chemodivergent Synthesis of Polycyclic Aromatic Diarylamines and Carbazoles by Thermal/Photochemical Process-Controlled Dephosphinylative Functionalizations of Amino(phosphinyl)arenes

Yasuhiro Okuda,  Takuma Sato,  Sou Takebe,  Matsuri Mori,  Mayo Fujimoto,  Kazunori Masuda, Taisei Sabato, Kan Wakamatsu, Haruo Akashi, Akihiro Orita

A chemodivergent synthesis of polycyclic aromatic diarylamines and carbazoles was established by employing thermally or photochemically controlled processes using KOtBu/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. However, when the reaction was performed under the illumination of purple light (LEDs, λmax = ca. 390 nm), KOtBu/1,10-phenanthroline promoted single-electron-transfer-triggered dephosphinylation followed by cyclization, producing the corresponding π-expanded carbazoles. We successfully synthesized a highly π-expanded dicarbazole through a dual dephosphinylative cyclization. Additionally, we present the optical properties of a series of amino compounds produced through the dephosphinylative processes.

The Journal of Organic Chemistry

The American Chemical Society (ACS)

89

11

7747

7757

10.1021/acs.joc.4c00432