Visible-Light-Promoted α-C(sp³)–H Amination of Ethers with Azoles and Amides

Abstract

A visible-light-induced highly efficient C(sp 3 )−H amination of ethers with amides and azoles has been presented under mild conditions via a nitrogen-and carbon-centered radical coupling process. This protocol successfully utilizes 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) and tert-butyl nitrite (TBN) as cocatalysts to deliver the aminated products of ethers under aerobic conditions. Notably, the developed reaction features the corresponding products in good yields (up to 93%) with a wide substrate scope. The mechanistic study indicates that C−N bond formation proceeds via a direct radical cross-coupling process. Preliminary biological activity analysis indicates that the resulting products have good and selective inhibitory activity on osteosarcoma (OS) cell lines and are promising for use as hits for drug discovery.

Iodine-catalyzed intermolecular 1,2-thio (seleno)amination of alkenes with 1,2,3-triazoles and disulfides (diselenides) in air

“…In the quenching reaction with another radical scavenger, butylated hydroxytoluene (BHT), product 4a was also suppressed completely. Nevertheless, a N 2 -selective BHT-adduct 8 could be detected by LC-MS, of which the N 2 -regioisomer structure could be deduced from our previous research result 23 (Scheme 6b and Scheme S4†). These phenomena indicated that this reaction proceeded via a radical.…”