Experimental and Computational Study of an Unexpected Iron-Catalyzed Carboetherification by Cooperative Metal and Ligand Substrate Interaction and Proton Shuttling
Azofra Mesa, Luis
Jang, Yoon Kyung
KAUST DepartmentChemical Science Program
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Online Publication Date2017-10-24
Print Publication Date2017-11-20
Permanent link to this recordhttp://hdl.handle.net/10754/626621
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AbstractAn 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.
CitationEl-Sepelgy O, Brzozowska A, Azofra LM, Jang YK, Cavallo L, et al. (2017) Experimental and Computational Study of an Unexpected Iron-Catalyzed Carboetherification by Cooperative Metal and Ligand Substrate Interaction and Proton Shuttling. Angewandte Chemie International Edition 56: 14863–14867. Available: http://dx.doi.org/10.1002/anie.201708240.
SponsorsL.M.A. and L.C. acknowledge King Abdullah University of Science and Technology (KAUST) for support. Gratitude is also due to the KAUST Supercomputing Laboratory for providing the computational resources (use of the supercomputer Shaheen II).