Research output: Contribution to journal › Article › peer-review
How Strong is Hydrogen Bonding to Amide Nitrogen? / Mikshiev, Vladimir Y.; Pozharskii, Alexander F.; Filarowski, Alexander; Novikov, Alexander S.; Antonov, Alexander S.; Tolstoy, Peter M.; Vovk, Mikhail A.; Khoroshilova, Olesya V.
In: ChemPhysChem, Vol. 21, No. 7, 02.04.2020, p. 651-658.Research output: Contribution to journal › Article › peer-review
}
TY - JOUR
T1 - How Strong is Hydrogen Bonding to Amide Nitrogen?
AU - Mikshiev, Vladimir Y.
AU - Pozharskii, Alexander F.
AU - Filarowski, Alexander
AU - Novikov, Alexander S.
AU - Antonov, Alexander S.
AU - Tolstoy, Peter M.
AU - Vovk, Mikhail A.
AU - Khoroshilova, Olesya V.
PY - 2020/4/2
Y1 - 2020/4/2
N2 - The protonation of the carboxamide nitrogen atom is an essential part of in vivo and in vitro processes (cis-trans isomerization, amides hydrolysis etc). This phenomenon is well studied in geometrically strongly distorted amides, although there is little data concerning the protonation of undistorted amides. In the latter case, the participation of amide nitrogen in hydrogen bonding (which can be regarded as the incipient state of a proton transfer process) is less well-studied. Thus, it would be a worthy goal to investigate the enthalpy of this interaction. We prepared and investigated a set of peri-substituted naphthalenes containing the protonated dimethylamino group next to the amide nitrogen atom (“amide proton sponges”), which could serve as models for the study of an intramolecular hydrogen bond with the amide nitrogen atom. X-Ray analysis, NMR spectra, basicity values as well as quantum chemical calculations revealed the existence of a hydrogen bond with the amide nitrogen, that should be attributed to the borderline between moderate and weak intramolecular hydrogen bonds (2–7 kcal ⋅ mol−1).
AB - The protonation of the carboxamide nitrogen atom is an essential part of in vivo and in vitro processes (cis-trans isomerization, amides hydrolysis etc). This phenomenon is well studied in geometrically strongly distorted amides, although there is little data concerning the protonation of undistorted amides. In the latter case, the participation of amide nitrogen in hydrogen bonding (which can be regarded as the incipient state of a proton transfer process) is less well-studied. Thus, it would be a worthy goal to investigate the enthalpy of this interaction. We prepared and investigated a set of peri-substituted naphthalenes containing the protonated dimethylamino group next to the amide nitrogen atom (“amide proton sponges”), which could serve as models for the study of an intramolecular hydrogen bond with the amide nitrogen atom. X-Ray analysis, NMR spectra, basicity values as well as quantum chemical calculations revealed the existence of a hydrogen bond with the amide nitrogen, that should be attributed to the borderline between moderate and weak intramolecular hydrogen bonds (2–7 kcal ⋅ mol−1).
KW - amides
KW - basicity
KW - hydrogen bonds
KW - proton sponge
KW - protonation
KW - ENERGY
KW - ACTIVE-SITE
KW - MOLECULAR-STRUCTURE
KW - STRUCTURAL-CHARACTERIZATION
KW - BASICITY
KW - MODEL
KW - PROTON SPONGES
KW - RESONANCE
KW - CIS-TRANS ISOMERIZATION
KW - DERIVATIVES
UR - http://www.scopus.com/inward/record.url?scp=85079234990&partnerID=8YFLogxK
U2 - 10.1002/cphc.201901104
DO - 10.1002/cphc.201901104
M3 - Article
AN - SCOPUS:85079234990
VL - 21
SP - 651
EP - 658
JO - Chemphyschem : a European journal of chemical physics and physical chemistry
JF - Chemphyschem : a European journal of chemical physics and physical chemistry
SN - 1439-4235
IS - 7
ER -
ID: 51803841