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Experimental and Computational Study of an Unexpected Iron‐Catalyzed Carboetherification by Cooperative Metal and Ligand Substrate Interaction and Proton Shuttling
Author(s) -
ElSepelgy Osama,
Brzozowska Aleksandra,
Azofra Luis Miguel,
Jang Yoon Kyung,
Cavallo Luigi,
Rueping Magnus
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201708240
Subject(s) - deprotonation , isomerization , protonation , ligand (biochemistry) , chemistry , catalysis , cycloisomerization , substrate (aquarium) , pyranose , proton , metal , photochemistry , stereochemistry , computational chemistry , organic chemistry , physics , ion , biochemistry , oceanography , receptor , quantum mechanics , geology
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.