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Experimental and Computational Exploration of para ‐Selective Silylation with a Hydrogen‐Bonded Template
Author(s) -
Maji Arun,
Guin Srimanta,
Feng Sheng,
Dahiya Amit,
Singh Vikas Kumar,
Liu Peng,
Maiti Debabrata
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.201708449
Subject(s) - regioselectivity , silylation , hydrogen bond , chemistry , selectivity , toluene , substrate (aquarium) , combinatorial chemistry , computational chemistry , molecule , catalysis , organic chemistry , oceanography , geology
The regioselective conversion of C−H bonds into C−Si bonds is extremely important owing to the natural abundance and non‐toxicity of silicon. Classical silylation reactions often suffer from poor functional group compatibility, low atom economy, and insufficient regioselectivity. Herein, we disclose a template‐assisted method for the regioselective para silylation of toluene derivatives. A new template was designed, and the origin of selectivity was analyzed experimentally and computationally. An interesting substrate–solvent hydrogen‐bonding interaction was observed. Kinetic, spectroscopic, and computational studies shed light on the reaction mechanism. The synthetic significance of this strategy was highlighted by the generation of a precursor of a potential lipophilic bioisostere of γ‐aminobutyric acid (GABA), various late‐stage diversifications, and by mimicking enzymatic transformations.