Premium
Hydrogen‐Bonding Thiourea Organocatalysts: The Privileged 3,5‐Bis(trifluoromethyl)phenyl Group
Author(s) -
Lippert Katharina M.,
Hof Kira,
Gerbig Dennis,
Ley David,
Hausmann Heike,
Guenther Sabine,
Schreiner Peter R.
Publication year - 2012
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.201200739
Subject(s) - chemistry , trifluoromethyl , thiourea , organocatalysis , hydrogen bond , lewis acids and bases , catalysis , frustrated lewis pair , nuclear magnetic resonance spectroscopy , molecule , solvent , density functional theory , trifluoromethylation , computational chemistry , medicinal chemistry , organic chemistry , enantioselective synthesis , alkyl
We present evidence that the privileged use of the 3,5‐bis(trifluoromethyl)phenyl group in thiourea organocatalysis is due to the involvement of the ortho ‐CH bond in the binding event with Lewis‐basic sites. We utilized a combination of low‐temperature IR spectroscopy, 2D NMR spectroscopy, nano‐MS (ESI) investigations, as well as density functional theory computations [M06/6‐31+G( d , p ), including solvent corrections as well as natural bond orbital and atoms‐in‐molecules analyses] to support our conclusions that bear implications for catalyst design.