Visible-Light-Induced C(sp²)–P Bond Formation by Denitrogenative Coupling of Benzotriazoles with Phosphites

Abstract

A visible-light-induced denitrogenative phosphorylation of benzotriazoles is presented, in which diverse substituted aryl phosphonates could be obtained in good to excellent yields. This efficient protocol exhibits good tolerance with various functional groups. Furthermore, the utility of this photochemical protocol is demonstrated by a gram-scale reaction, and a reasonable mechanism is proposed.

Visible light-mediated C P bond formation reactions

“…Apart from aryl bromides, aryl chlorides and aryl triflates are suitable for the transformation. A similar elegant work was also realized by Xia and coworkers [74] by using benzotriazoles as aryl radical precursors (Scheme 16b). Very recently, Lakhdar group [75] reported a visible light-promoted synthesis of aryl phosphonates from diaryliodonium salts with phosphites under photoredox catalyst free conditions (Scheme 16c).…”

A Visible‐Light‐Promoted Metal‐Free Strategy towards Arylphosphonates: Organic‐Dye‐Catalyzed Phosphorylation of Arylhydrazines with Trialkylphosphites

“…Only limited examples concerning using photoredox catalysis to synthesize organophosphorus compounds have been reported over the past five years . Xia et al developed a photocatalytic method for the C( sp 2 )−P bond formation via a denitrogenative coupling of benzotriazoles with phosphites catalyzed by a iridium polypyridyl complex . Two novel synthetic methodologies, by using ruthenium polypyridyl complexes as visible‐light photoredox catalysis for the synthesis of arylphosphonates, were reported successively by Toste et al (Scheme b) and König et al (Scheme c) .…”

Recent Developments on Denitrogenative Functionalization of Benzotriazoles

“…More recently, Yang and co-workers developed the visible-light-induced denitrogenative phosphorylation of benzotriazoles with phosphites under mild conditions (Scheme 32). 26 A series of ortho-phosphorylated N-arylbenzamides was obtained in good to excellent yields. In addition, this reaction exhibited excellent functional group tolerance.…”