Synthesis of Carboranylated Dihydropyrrolo[1,2- a]quinoxalines and Dihydroindolo[1,2- a]quinoxalines by BF3·OEt2-Catalyzed Heterocyclization of C-Formyl- o-carboranes and Investigation of Their Oxidation Stability

J Org Chem. 2024 Mar 1;89(5):3573-3579. doi: 10.1021/acs.joc.3c02443. Epub 2024 Feb 20.

Abstract

A BF3·OEt2-catalyzed synthesis of carboranylated dihydropyrrolo[1,2-a]quinoxalines and dihydroindolo[1,2-a]quinoxalines in 30-99% yields is presented through the heterocyclization of various C-modified C-formyl-o-carboranes with 1-(2-aminophenyl)-pyrroles/indoles. A systematic comparative investigation of their oxidation stability in air confirmed that 4-carboranyl-4,5-dihydropyrrolo[1,2-a]quinoxaline had better stability than the 4-phenyl analogue. A cage-deboronation reaction for N-acetyl-substituted carboranylated dihydropyrrolo[1,2-a]quinoxaline produced the corresponding 7,8-nido-carborane cesium salt. A kinetic resolution was also realized to obtain an optically pure carboranylated N-heterocycle scaffold bearing a carborane cage carbon-bonded chiral stereocenter.