Experimental and Computational Study of an Unexpected Iron‐Catalyzed Carboetherification by Cooperative Metal and Ligand Substrate Interaction and Proton Shuttling. (24th October 2017)

• Record Type: Journal Article
• Authors: El‐Sepelgy, Osama; Brzozowska, Aleksandra; Azofra, Luis Miguel; Jang, Yoon Kyung; Cavallo, Luigi; Rueping, Magnus
• Is Part Of: Angewandte Chemie. Volume 129:Number 47(2017)
• Page Start: 15059
• Page End: 15063
• Publication Date: 2017-10-24
• Subjects: Carboveretherung -- Eisenkatalyse -- Enolether -- Heterocyclen -- Synthesemethoden; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201708240
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: An iron‐catalyzed cycloisomerization of allenols to deoxygenated pyranose glycals has been developed. Combined experimental and computational studies show that the iron complex exhibits a dual catalytic role in that the non‐innocent cyclopentadienone ligand acts as proton shuttle by initial hydrogen abstraction from the alcohol and by facilitating protonation and deprotonation events in the isomerization and demetalation steps. Molecular orbital analysis provides insight into the unexpected and selective formation of the 3, 4‐dihydro‐2 H ‐pyran.