Controlling the conformation of arylamides: computational studies of intramolecular hydrogen bonds between amides and ethers or thioethers

Chemistry : a European Journal
Robert J DoerksenMichael L Klein

Abstract

The role of an ortho-alkylthioether group in controlling the conformation around the ring-N bonds of meta-connected arylamide oligomers is studied. Density functional theory (DFT) geometries of model compounds, including acetanilide, an ether acetanilide, and a thioether acetanilide, and their corresponding diamides, show that for either monoamide or diamide the alkyl side chain of the thioether should be perpendicular to the aryl plane, whereas for the ether monoamide, the alkyl side chain is in the aryl plane. DFT ring-N torsional potentials and constrained geometries of the model compounds demonstrate that carbonyl-S repulsion leads to a high torsional barrier and that intramolecular N-H...S and C-H...O hydrogen bonds and ring-amide conjugation lead to N-H having a preferred orientation in the benzene plane pointing towards S. The N-H bond lengthens and the ortho-ring C-H bond shortens in a regular pattern in the approach to the preferred orientation. Calculated IR frequencies for the N-H stretch show a clear red shift between model compounds without and with the thioether side chain.

Citations

Jun 17, 2005·Journal of Industrial Microbiology & Biotechnology·Jason RennieGregory N Tew
Apr 11, 2009·Proceedings of the National Academy of Sciences of the United States of America·Sungwook ChoiWilliam F DeGrado
Aug 17, 2011·Antimicrobial Agents and Chemotherapy·Bruk MensaWilliam F DeGrado
Apr 18, 2007·Nature Chemical Biology·Catherine M GoodmanWilliam F DeGrado
Jun 21, 2006·Chemical Communications : Chem Comm·Thierry BuffeteauIvan Huc
Aug 21, 2015·Expert Opinion on Drug Discovery·István M Mándity, Ferenc Fülöp
Nov 11, 2008·Current Opinion in Biotechnology·Richard W ScottGregory N Tew
Mar 5, 2008·Biopolymers·Abhigyan SomGregory N Tew
Apr 25, 2006·Journal of Computational Chemistry·Satyavani VemparalaMichael L Klein
Jun 15, 2013·Physical Chemistry Chemical Physics : PCCP·Jhenny F GalanVojislava Pophristic
May 18, 2007·The Journal of Physical Chemistry. a·Laurent DucasseThierry Buffeteau
Oct 1, 2010·The Journal of Physical Chemistry. B·Marcin BroniatowskiJarosław Majewski
Aug 9, 2012·Chemical Reviews·Dan-Wei ZhangZhan-Ting Li
Dec 22, 2006·The Journal of Physical Chemistry. a·Peter I Nagy, Paul W Erhardt

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