Journal of Physical Chemistry A p. 909 - 915 (2018)
Update date:2022-08-31
Topics:
Emenike, Bright U.
Spinelle, Ronald A.
Rosario, Ambar
Shinn, David W.
Yoo, Barney
CH-π aromatic interactions are ubiquitous in nature and are capable of regulating important chemical and biochemical processes. Solvation and aromatic substituent effects are known to perturb the CH-π aromatic interactions. However, the nature by which the two factors influence one another is relatively unexplored. Here we demonstrate experimentally that there is a quantitative correlation between substituent effects in CH-π interactions and the hydrogen-bond acceptor constants of the solvating molecule. The CH-π interaction energies were measured by the conformational study of a series of aryl-substituted molecular balances in which the conformational preferences depended on the relative strengths of the methyl and aryl CH-π interactions in the folded and unfolded states, respectively. Due to the favorable methyl-aromatic interactions, the balances were found to exist predominantly in the folded state. The observed substituent effect in the conformational preferences of the balances was controlled by the explicit solvation/desolvation of the aryl proton. The interpretation of the conformational free energy as a function of substituents and solvation using Hunter's solvation model revealed that a linear relationship exists between the sensitivity of aromatic substituent effects (i.e., the ρ values derived from Hammett plots) and the hydrogen-bond acceptor propensity (βs) of the solvent molecule: ρ = 0.06βs - 0.04.
View MoreTaizhou Chemedir Biopharm-tech Co., Ltd
Contact:+86 523 86200218
Address:G09, No. 1 Avenue China Medical City, Taizhou,Jiangsu, China
WUHU HUAHAI BIOLOGY ENGINEERING CO LTD
Contact:+86-553-3836920
Address:7/F NO.82 LAODONG ROAD WUHU CHINA
Taizhou YOJOY Chemical Co., Ltd.
Contact:13857143241
Address:Yangfu Industrial Park, Xianju, Zhejiang, P. R. China
Shanghai Bojing Chemical Co., Ltd.
Contact:021-37122233
Address:6F Buildiing 11,No.388,Baifu Road,District Fengxian.Shanghai, China.
Jinan Yijialian Economic and Trade Development Co., Ltd.
Contact:+86 0531-66729596
Address:jinan
Doi:10.1021/jo01159a004
(1948)Doi:10.1016/j.bmcl.2010.06.078
(2010)Doi:10.1002/anie.200701551
(2007)Doi:10.1021/jo201830b
(2011)Doi:10.1021/ol991373b
(2000)Doi:10.1021/acs.orglett.6b03468
(2017)