3 years ago

Experimental and Computational Study of an Unexpected Iron-Catalyzed Carboetherification by Cooperative Metal and Ligand Substrate Interaction and Proton Shuttling

Experimental and Computational Study of an Unexpected Iron-Catalyzed Carboetherification by Cooperative Metal and Ligand Substrate Interaction and Proton Shuttling
Luigi Cavallo, Magnus Rueping, Luis Miguel Azofra, Aleksandra Brzozowska, Osama El-Sepelgy, Yoon Kyung Jang
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-2H-pyran. Not as innocent as it looks: Allenols underwent cycloisomerization to deoxygenated pyranose glycals in the presence of an iron complex, the cyclopentadienone ligand of which acted as proton shuttle to facilitate protonation and deprotonation events in the isomerization and demetalation steps (see scheme). Molecular orbital analysis provided insight into the unexpected and selective formation of the 3,4-dihydro-2H-pyran products.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201708240

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