Silver‐Catalyzed Oxidative C(sp3)−P Bond Formation through C−C and P−H Bond Cleavage

• Published in: Angewandte Chemie International Edition Vol. 56; no. 35; pp. 10539 - 10544
• Main Authors: Li, Lili, Huang, Wenbin, Chen, Lijin, Dong, Jiaxing, Ma, Xuebing, Peng, Yungui
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 21-08-2017
• Edition: International ed. in English
• Subjects: 1,3-dicarbonyl compounds; C(sp3)−P bond formation; Cleavage; Coupling (molecular); Cross coupling; C−C bond cleavage; Phosphonates; Selectivity; Silver; cross-coupling; silver; C(sp3)−P bond formation; 1,3-dicarbonyl compounds; C−C bond cleavage
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201704910

The silver‐catalyzed oxidative C(sp3)−H/P−H cross‐coupling of 1,3‐dicarbonyl compounds with H‐phosphonates, followed by a chemo‐ and regioselective C(sp3)−C(CO) bond‐cleavage step, provided heavily functionalized β‐ketophosphonates. This novel method based on a readily available reaction system exhibits wide scope, high functional‐group tolerance, and exclusive selectivity.
A silver trigger: A wide range of β‐ketophosphonates were synthesized readily by a silver‐catalyzed transformation involving the oxidative C(sp3)−H/ P−H cross‐coupling of 1,3‐dicarbonyl compounds with H‐phosphonates and tandem exclusive C(sp3)−C(CO) bond cleavage (see scheme). The base‐, ligand‐, and additive‐free procedure has the additional advantages of a simple catalyst system and good functional‐group tolerance.