TY - JOUR
T1 - Effects of introduction of α-carboxylate, N-methyl, and N-formyl groups on intramolecular cyclization of o-quinone amines
T2 - Density functional theory-based study
AU - Kishida, Ryo
AU - Saputro, Adhitya Gandaryus
AU - Arevalo, Ryan Lacdao
AU - Kasai, Hideaki
N1 - Funding Information:
This work is supported in part by: MEXT Grant-in-Aid for Scientific Research (15H05736, 24246013, 15KT0062, 26248006); Grant-in-Aid for JSPS Research Fellow (17J01276); JST ACCEL Program (JPMJAC1501) “Creation of the Functional Materials on the Basis of the Inter-Element-Fusion Strategy and their Innovative Applications”; and NEDO Project “R&D Toward Realizing an Innovative Energy Saving Hydrogen Society based on Quantum Dynamics Applications.” Some of the numerical calculations presented here done using the computer facilities at the following institutes: CMC (Osaka University), ISSP, KEK, NIFS, and YITP. The authors thank Dr. Wilson Agerico Tan Diño for his interest in this research and for continuous support.
Funding Information:
This work is supported in part by: MEXT Grant-in-Aid for Scientific Research (15H05736, 24246013, 15KT0062, 26248006); Grant-in-Aid for JSPS Research Fellow (17J01276); JST ACCEL Program (JPMJAC1501) “Creation of the Functional Materials on the Basis of the Inter-Element-Fusion Strategy and their Innovative Applications”; and NEDO Project “R&D Toward Realizing an Innovative Energy Saving Hydrogen Society based on Quantum Dynamics Applications.”
Publisher Copyright:
© 2017 Wiley Periodicals, Inc.
PY - 2017/12/5
Y1 - 2017/12/5
N2 - o-Quinone amines, which are relevant to various biological processes, can undergo spontaneous intramolecular cyclization (ring closure reaction by amino-terminated hydrocarbon side chain) that deactivates them toward another possible reactions, that is, thiol binding. Density functional theory-based calculation is employed for obtaining the potential energy curves along the CN bond formation in the intramolecular cyclization of various o-quinone amines, viz., dopaminequinone, dopaquinone, N-methyl-dopaminequinone, N-formyl-dopaminequinone, and the corresponding methylene-inserted analogues. The activation barrier is decreased by introduction of α-carboxylate and N-methyl group whereas increased by introduction of N-formyl group. A negative correlation between the activation barriers and the level of highest occupied molecular orbital is pointed out. Furthermore, the methylene-inserted analogues show decreased activation barriers. This is explained by reduction of steric repulsion in the transition state.
AB - o-Quinone amines, which are relevant to various biological processes, can undergo spontaneous intramolecular cyclization (ring closure reaction by amino-terminated hydrocarbon side chain) that deactivates them toward another possible reactions, that is, thiol binding. Density functional theory-based calculation is employed for obtaining the potential energy curves along the CN bond formation in the intramolecular cyclization of various o-quinone amines, viz., dopaminequinone, dopaquinone, N-methyl-dopaminequinone, N-formyl-dopaminequinone, and the corresponding methylene-inserted analogues. The activation barrier is decreased by introduction of α-carboxylate and N-methyl group whereas increased by introduction of N-formyl group. A negative correlation between the activation barriers and the level of highest occupied molecular orbital is pointed out. Furthermore, the methylene-inserted analogues show decreased activation barriers. This is explained by reduction of steric repulsion in the transition state.
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U2 - 10.1002/qua.25445
DO - 10.1002/qua.25445
M3 - Article
AN - SCOPUS:85031742535
VL - 117
JO - International Journal of Quantum Chemistry
JF - International Journal of Quantum Chemistry
SN - 0020-7608
IS - 23
M1 - e25445
ER -