methyl groups
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2022 ◽  
pp. 1-9
Nan Lu ◽  
Hui Liang ◽  
Chengxia Miao ◽  
Xiaozheng Lan ◽  
Ping Qian

The mechanism for DMAP-promoted [4 + 2]-annulation of prop-2-ynylsulfonium with isatoic anhydride is investigated using the M06-2X functional. The reaction comprises isomerization of prop-2-ynylsulfonium in stage 1. Stage 2 includes DMAP-promoted deprotonation, nucleophilic addition, ring opening, and decarboxylation. Three steps of intramolecular cycloaddition, DMAP-promoted protonation, and dealkylation occur in stage 3, generating methylated DMAP and neutral thioether, which undergo double-bond isomerization to yield 3-methylthio-4-quinolone. The ability of DMAP to promote the reaction lies in the barrier decrease for alkyne isomerization, deprotonation/protonation of allenes, and dealkylation as effective bases for transferring protons and methyl groups. The roles of prop-2-ynylsulfonium and isatoic anhydride were demonstrated to be C2 and C4 synthons via Multiwfn analysis on the frontier molecular orbital. An alternative path was also confirmed by the Mayer bond order of the vital transition states.

Materials ◽  
2022 ◽  
Vol 15 (2) ◽  
pp. 475
Mariela M. Nolasco ◽  
Paulo J. A. Ribeiro-Claro ◽  
Pedro D. Vaz

The structure and dynamics of crystalline 4-(dimethylamino) benzaldehyde, 4DMAB, are assessed through INS spectroscopy combined with periodic DFT calculations. The excellent agreement between experimental and calculated spectra is the basis for a reliable assignment of INS bands. The external phonon modes of crystalline 4DMAB are quite well described by the simulated spectrum, as well as the modes involving low-frequency molecular vibrations. Crystal field splitting is predicted and observed for the modes assigned to the dimethylamino group. Concerning the torsional motion of methyl groups, four individual bands are identified and assigned to specific methyl groups in the asymmetric unit. The torsional frequencies of the four methyl groups in the asymmetric unit fall in a region of ca. 190 ± 20 cm−1, close to the range of values observed for methyl groups bonding to unsaturated carbon atoms. The hybridization state of the X atom in X-CH3 seems to play a key role in determining the methyl torsional frequency.

2022 ◽  
Vol 9 ◽  
Gerd Gleixner

We determined the kinetic isotope effect on the serine hydroxymethyltransferase reaction (SHMT), which provides important C1 metabolites that are essential for the biosynthesis of DNA bases, O-methyl groups of lignin and methane. An isotope effect on the SHMT reaction was suggested being responsible for the well-known isotopic depletion of methane. Using the cytosolic SHMT from pig liver, we measured the natural carbon isotope ratios of both atoms involved in the bond splitting by chemical degradation of the remaining serine before and after partial turnover. The kinetic isotope effect 13(VMax/Km) was 0.994 0.006 and 0.995 0.007 on position C-3 and C-2, respectively. The results indicated that the SHMT reaction does not contribute to the 13C depletion observed for methyl groups in natural products and methane. However, from the isotopic pattern of caffeine, isotope effects on the methionine synthetase reaction and on reactions forming Grignard compounds, the involved formation and fission of metal organic bonds are likely responsible for the observed general depletion of “activated” methyl groups. As metal organic bond formations in methyl transferases are also rate limiting in the formation of methane, they may likely be the origin of the known 13C depletion in methane.

2022 ◽  
Yasuyuki Yamada ◽  
Chee-Ming Teoh ◽  
Yuka Toyoda ◽  
Kentaro Tanaka

Direct catalytic hydroxylation of benzene under mild reaction conditions proceeded efficiently in the presence of a monocationic μ-nitrido-bridged iron phthalocyanine dimer with 16 peripheral methyl groups in an acetonitrile solution...

2022 ◽  
Yujian Mao ◽  
Jing Jiang ◽  
Dandan Yuan ◽  
Xiuzhen Chen ◽  
Yanan Wang ◽  

Methyl groups widely exist in bioactive molecules and site-specific methylation becomes a valuable strategy for their structural functionalization. Aiming to introduce this smallest alkyl handle, a high regioselective peri- and...

2021 ◽  
Jinggang Lan ◽  
Yo-ichi Yamamoto ◽  
Toshinori Suzuki ◽  
Vladimir Rybkin

We present condensed-phase first-principles molecular dynamics simulations to elucidate the presence of different electron trapping sites in liquid methanol and their roles in the formation, electronic transitions, and relaxation of solvated electrons (e−met) in methanol. Excess electrons injected into liquid methanol are most likely trapped by methyl groups, but rapidly diffuse to more stable trapping sites with dangling OH bonds. After localization at the sites with one free OH bond (1OH trapping sites), reorientation of other methanol molecules increases the OH coordination number and the trap depth, and ultimately four OH bonds become coordinated with the excess electrons under thermal conditions. The simulation identified four distinct trapping states with different OH coordination numbers. The simulation results also revealed that electronic transitions of e−met are primarily due to charge transfer between electron trapping sites (cavities) formed by OH and methyl groups and that these transitions differ from hydrogenic electronic transitions involving aqueous solvated electrons (e−aq). Such charge transfer also explains the alkyl-chain-length dependence of the photoabsorption peak wavelength and the excited-state lifetime of solvated electrons in primary alcohols.

Biomolecules ◽  
2021 ◽  
Vol 11 (12) ◽  
pp. 1911
Hans Felix Staehle ◽  
Heike Luise Pahl ◽  
Jonas Samuel Jutzi

Histone methylation tightly regulates chromatin accessibility, transcription, proliferation, and cell differentiation, and its perturbation contributes to oncogenic reprogramming of cells. In particular, many myeloid malignancies show evidence of epigenetic dysregulation. Jumonji C (JmjC) domain-containing proteins comprise a large and diverse group of histone demethylases (KDMs), which remove methyl groups from lysines in histone tails and other proteins. Cumulating evidence suggests an emerging role for these demethylases in myeloid malignancies, rendering them attractive targets for drug interventions. In this review, we summarize the known functions of Jumonji C (JmjC) domain-containing proteins in myeloid malignancies. We highlight challenges in understanding the context-dependent mechanisms of these proteins and explore potential future pharmacological targeting.

A. S. Panasyugin ◽  
N. D. Pavlovskiy ◽  
N. P. Masherova ◽  
A. R. Tsyganov ◽  
I. I. Kurilo

The purpose of this work is to study the process of neutralization of vapors of a mixed solvent of the brand 650 by the adsorption‑catalytic method. The essence of the method consists in the concentration of solvent components on the sorbent, thermal desorption followed by periodic flameless catalytic oxidation of accumulated organic substances to carbon dioxide and water. Synthetic zeolite of the NaX brand was used as a sorbent, and a porous material based on foam ceramics of the Al2O3/SiO2 composition with a highly developed modified surface with an active catalytic phase was used as a catalyst. The mixed solvent contains, xylenes, ethylcellosol, n‑butanol. It is shown that the value of the sorption volume of zeolite for each class of the considered compounds is influenced by certain factors: the length and structure of the carbon skeleton, the position of the hydroxyl group (for alcohols and esters), the number of methyl groups in the composition of molecules (for the production of benzene). The conversion rate of the mixed solvent components was 65.4–90.1 %.

2021 ◽  
Shelby Brooks Mills ◽  
Meredith B Mock ◽  
Ryan M Summers

Methylxanthines have a rich history as therapeutics and pharmaceuticals. However, natural dimethyl- and monomethylxanthines are difficult to produce synthetically, which has limited further exploration of these compounds in medicinal applications. A biosynthetic method for production of methylxanthines from whole cell biocatalysts is an attractive alternative. The bacterium Pseudomonas putida CBB5 contains a set of five enzymes, NdmABCDE, which are responsible for methylxanthine metabolism via N-demethylation to xanthine. The recent elucidation of the crystal structures of NdmA and NdmB, which remove the N1- and N3- methyl groups of caffeine, respectively, has opened new avenues to create biocatalysts for methylxanthine production. We have created a set of fifteen N-demethylase mutants and expressed them in E. coli BL21(DE3) as whole cell biocatalysts. The activity of each mutant was characterized for their affinity towards caffeine, theobromine, and theophylline. Two mutant enzymes in particular, labeled NdmA3 and NdmA4, both exhibited selectivity towards the N3-methyl group instead of the N1-methyl group. We also discovered that specific point mutations in NdmD resulted in the ability to tune the rate of the N-demethylase reaction. These new enzymes provide the capability of producing high-value methylxanthines, such as paraxanthine and 1-methylxanthine, through a biocatalytic route.

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