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DFT calculation and NMR data of novel aryloxymaleimides and the intermediates and transition states in the reaction.

ABSTRACT: Maleimide ring is an important scaffold in organic chemistry, and tosyloxy group is a functional group widely used in organic synthesis. Nevertheless, tosyloxymaleimide compounds have been rarely reported, and the reactivity properties and potential applications of tosyloxymaleimide in organic synthesis remain to be explored. This article presents the density functional theory (DFT) calculation data of the reaction mechanism of nucleophilic substitutions of tosyloxymaleimide with phenol, including the coordinate of all the stationary points (the reactant, transition states, intermediates, and product). All the structures had been geometrically optimized using M06-2X functional and 6-31+G** basis set; the reactant, intermediates and product had no imaginary frequencies, and each transition state has only one imaginary frequency in the vibration analysis at the same computation level. The intrinsic reaction coordinates (IRCs) of two steps of the reaction were calculated. ¹H and ¹³C NMR spectra of the novel aryloxymaleimide compounds synthesized using this nucleophilic substitution reaction (doi: 10.1016/j.molstruc.2019.04.020 Yan et al.,) were also presented in this article.

SUBMITTER: Yan M

PROVIDER: S-EPMC6597784 | biostudies-literature | 2019 Aug

REPOSITORIES: biostudies-literature

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DFT calculation and NMR data of novel aryloxymaleimides and the intermediates and transition states in the reaction.

Yan Maocai M Zhang Zhen Z Zhou Jinhui J Li Wei W Zhang Chunyan C Fan Shuai S Yang Zhaoyong Z

Data in brief 20190608

Maleimide ring is an important scaffold in organic chemistry, and tosyloxy group is a functional group widely used in organic synthesis. Nevertheless, tosyloxymaleimide compounds have been rarely reported, and the reactivity properties and potential applications of tosyloxymaleimide in organic synthesis remain to be explored. This article presents the density functional theory (DFT) calculation data of the reaction mechanism of nucleophilic substitutions of tosyloxymaleimide with phenol, includi ...[more]

PMID: 31297419

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Project description:Pharanois phoborhodopsin (ppR) from Natronomonas pharaonis is a transmembrane photoreceptor protein involved in negative phototaxis. Structural changes in ppR triggered by photoisomerization of the retinal chromophore are transmitted to its cognate transducer protein (pHtrII) through a cyclic photoreaction pathway involving several photointermediates. This pathway is called the photocycle. It is important to understand the detailed configurational changes of retinal during the photocycle. We previously observed one of the photointermediates (M-intermediates) by in situ photoirradiation solid-state NMR experiments. In this study, we further observed the 13C cross-polarization magic-angle-spinning NMR signals of late photointermediates such as O- and N'-intermediates by illumination with green light (520 nm). Under blue-light (365 nm) irradiation of the M-intermediates, 13C cross-polarization magic-angle-spinning NMR signals of 14- and 20-13C-labeled retinal in the O-intermediate appeared at 115.4 and 16.4 ppm and were assigned to the 13-trans, 15-syn configuration. The signals caused by the N'-intermediate appeared at 115.4 and 23.9 ppm and were assigned to the 13-cis configuration, and they were in an equilibrium state with the O-intermediate during thermal decay of the M-intermediates at -60°C. Thus, photoirradiation NMR studies revealed the photoreaction pathways from the M- to O-intermediates and the equilibrium state between the N'- and O-intermediate. Further, we evaluated the detailed retinal configurations in the O- and N'-intermediates by performing a density functional theory chemical shift calculation. The results showed that the N'-intermediate has a 63° twisted retinal state due to the 13-cis configuration. The retinal configurations of the O- and N'-intermediates were determined to be 13-trans, 15-syn, and 13-cis, respectively, based on the chemical shift values of [20-13C] and [14-13C] retinal obtained by photoirradiation solid-state NMR and density functional theory calculation.

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DFT calculation and NMR data of novel aryloxymaleimides and the intermediates and transition states in the reaction.

Publications

DFT calculation and NMR data of novel aryloxymaleimides and the intermediates and transition states in the reaction.

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