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Effects of introduction of α-carboxylate, N-methyl, and N-formyl groups on intramolecular cyclization of o-quinone amines: Density functional theory-based study
Kishida R.a, Saputro A.G.b, Arevalo R.L.c, Kasai H.a,c
a Department of Applied Physics, Osaka University, Suita, Osaka, 565-0871, Japan
b Engineering Physics Research Group, Faculty of Industrial Technology, Institut Teknologi Bandung, Bandung, 40132, Indonesia
c National Institute of Technology, Akashi College, Akashi, Hyogo, 674-8501, Japan
[vc_row][vc_column][vc_row_inner][vc_column_inner][vc_separator css=”.vc_custom_1624529070653{padding-top: 30px !important;padding-bottom: 30px !important;}”][/vc_column_inner][/vc_row_inner][vc_row_inner layout=”boxed”][vc_column_inner width=”3/4″ css=”.vc_custom_1624695412187{border-right-width: 1px !important;border-right-color: #dddddd !important;border-right-style: solid !important;border-radius: 1px !important;}”][vc_empty_space][megatron_heading title=”Abstract” size=”size-sm” text_align=”text-left”][vc_column_text]© 2017 Wiley Periodicals, Inc.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.[/vc_column_text][vc_empty_space][vc_separator css=”.vc_custom_1624528584150{padding-top: 25px !important;padding-bottom: 25px !important;}”][vc_empty_space][megatron_heading title=”Author keywords” size=”size-sm” text_align=”text-left”][vc_column_text]Activation barriers,Highest occupied molecular orbital,Intramolecular cyclizations,Intramolecular reactions,Negative correlation,O-quinones,Potential energy curves,Ring closure reactions[/vc_column_text][vc_empty_space][vc_separator css=”.vc_custom_1624528584150{padding-top: 25px !important;padding-bottom: 25px !important;}”][vc_empty_space][megatron_heading title=”Indexed keywords” size=”size-sm” text_align=”text-left”][vc_column_text]cyclization,density functional theory,intramolecular reaction,o-quinone[/vc_column_text][vc_empty_space][vc_separator css=”.vc_custom_1624528584150{padding-top: 25px !important;padding-bottom: 25px !important;}”][vc_empty_space][megatron_heading title=”Funding details” size=”size-sm” text_align=”text-left”][vc_column_text][{‘$’: ‘This work is supported in part by: MEXT Grant-in-Aid for Scientific Research (15H05736, 24246013, 15KT0062, 26248006); Grant-in-Aid for JSPS Research Fellow (17J01276); JST ACCEL Program (JPMJAC1501) “Creation of the Functional Materials on the Basis of the Inter-Element-Fusion Strategy and their Innovative Applications”; and NEDO Project “R&D Toward Realizing an Innovative Energy Saving Hydrogen Society based on Quantum Dynamics Applications.” Some of the numerical calculations presented here done using the computer facilities at the following institutes: CMC (Osaka University), ISSP, KEK, NIFS, and YITP. The authors thank Dr. Wilson Agerico Tan Diño for his interest in this research and for continuous support.’}, {‘$’: ‘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.”’}][/vc_column_text][vc_empty_space][vc_separator css=”.vc_custom_1624528584150{padding-top: 25px !important;padding-bottom: 25px !important;}”][vc_empty_space][megatron_heading title=”DOI” size=”size-sm” text_align=”text-left”][vc_column_text]https://doi.org/10.1002/qua.25445[/vc_column_text][/vc_column_inner][vc_column_inner width=”1/4″][vc_column_text]Widget Plumx[/vc_column_text][/vc_column_inner][/vc_row_inner][/vc_column][/vc_row][vc_row][vc_column][vc_separator css=”.vc_custom_1624528584150{padding-top: 25px !important;padding-bottom: 25px !important;}”][/vc_column][/vc_row]