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Modulating Electrostatic Interactions in Ion Pair Intermediates To Alter Site Selectivity in the C−O Deoxygenation of Sugars
Author(s) -
Lowe Jared M.,
Bowers Bekah E.,
Seo Youngran,
Gagné Michel R.
Publication year - 2020
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.202007415
Subject(s) - deoxygenation , chemistry , selectivity , stereoselectivity , catalysis , borane , reactivity (psychology) , combinatorial chemistry , ion , toluene , anomer , computational chemistry , organic chemistry , medicine , alternative medicine , pathology
Controlling which products one can access from the predefined biomass‐derived sugars is challenging. Changing from CH 2 Cl 2 to the greener alternative toluene alters which C−O bonds in a sugar are cleaved by the tris(pentafluorophenyl)borane/HSiR 3 catalyst system. This increases the diversity of high‐value products that can be obtained through one‐step, high‐yielding, catalytic transformations of the mono‐, di‐, and oligosaccharides. Computational methods helped identify this non‐intuitive outcome in low dielectric solvents to non‐isotropic electrostatic enhancements in the key ion pair intermediates, which influence the reaction coordinate in the reactivity‐/selectivity‐determining step. Molecular‐level models for these effects have far‐reaching consequences in stereoselective ion pair catalysis.