Palladium‐Catalyzed Reductive Double Carbonylation of Nitroarenes with Aryl Halides Using Mo(CO)6 as a Reductant and Carbonyl Source. Issue 2 (3rd November 2022)

• Record Type: Journal Article
• Authors: Liu, Xueling; An, Tongshun; Yin, Zhiping; Zhang, Wenzhou
• Is Part Of: Chemistry. Volume 29:Issue 2(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-11-03
• Subjects: aryl halides -- benzoxazin-4-one -- carbonylation -- nitroarenes -- palladium; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202202880
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: A new palladium‐catalyzed reductive double carbonylation of nitroarenes with aryl halides for the synthesis of benzoxazin‐4‐ones has been reported. The key to success was the use of Mo(CO)6 as a reductant and bench‐stable solid carbonyl sources. Various aryl iodides, bromides, and trifluoromethanesulfonates are suitable reaction partners and produce corresponding benzoxazin‐4‐one derivatives in moderate to good yields. Preliminary mechanistic studies indicate that nitrosoarene was first generated as the key intermediate through nitro reduction. Remarkably, this method avoids the use of toxic CO gas and is further applied to the late‐stage modification of estrone. Abstract : The synthesis of benzoxazin‐4‐ones by palladium‐catalyzed reductive double carbonylation of nitroarenes with aryl halides has been achieved. The key to success was the use of Mo(CO)6 as a reductant and bench‐stable solid carbonyl source. Various aryl iodides, bromides, and trifluoromethanesulfonates are suitable reaction partners and produce corresponding nitrogen heterocycles in moderate to good yields. Notably, this method avoids the use of toxic CO gas and is further applied to the late‐stage modification of estrone.