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Investigation of Electrostatic Interactions towards Controlling Silylation‐Based Kinetic Resolutions
Author(s) -
Zhang Tian,
Redden Brandon K.,
Wiskur Sheryl L.
Publication year - 2019
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201900754
Subject(s) - chemistry , selectivity , steric effects , intermolecular force , silylation , alkyl , electronic effect , kinetic resolution , kinetic energy , electrostatics , computational chemistry , stereochemistry , enantioselective synthesis , organic chemistry , catalysis , molecule , physics , quantum mechanics
Electrostatic interactions between a silylated isothiourea intermediate and an ester π system were explored by determining how variations in sterics and electronics affect the selectivity of a silylation‐based kinetic resolution. Sterics on the π systems affect the selectivity factors of alkyl 2‐hydroxycyclohexanecarboxylates, resulting in a strong correlation of selectivity factors to Charton values. Induction effects of electron‐withdrawing substituents on phenyl esters significantly enhance selectivity supporting an edge to face π–π interaction. The linear free energy relationships that were uncovered will aid in future incorporation of intermolecular electrostatic interactions towards controlling asymmetric reactions.