Article
Chemistry, Multidisciplinary
Robert J. Mayer, Harpreet Kaur, Sophia A. Rauscher, Joseph Moran
Summary: Metal ions can catalyze transamination under biologically relevant conditions, with Cu2+, Ni2+, Co2+, and V5+ identified as the most active. These ions primarily accelerate the reaction by stabilizing key imine intermediates or increasing the acidity of the bound imine. Direct metal ion-catalyzed amino group transfer is highly favored even in the absence of cofactors or protein catalysts under biologically compatible reaction conditions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Weikang Dai, Maoshuai Li, Jie Wei, Qi Yang, Yi Feng, Cheng Yang, Wanxin Yang, Mei-Yan Wang, Xinbin Ma
Summary: The paper investigates the dissociation and anion mechanism for formaldehyde hydroformylation using DFT calculation and experimental study. It finds that HCHO insertion into the Rh-H bond is the rate-controlling step in the dissociation mechanism, while the nucleophilic addition of HCHO to the HOCH2-Rh species is more energetically favorable in the anion mechanism. The research also suggests that the strong electron-donating ligand could lead to higher reactivity in the anion mechanism, providing insights for improving selectivity in the reaction.
JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Applied
Wei Zhang, Guang-Jie Xia, Yang-Gang Wang
Summary: In this study, density functional theory calculations were used to investigate the mechanisms of methanol electro-oxidation reaction catalyzed by Pt, PtCu alloy, and Cu. The results showed that alloying Pt with Cu can enhance the reaction activity by reducing the energy barrier for CO* and OH* binding and promoting water dissociation to generate more OH*.
CHINESE JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Physical
Takanori Iwasaki, Wataru Ishiga, Shrinwantu Pal, Kyoko Nozaki, Nobuaki Kambe
Summary: This study presents a mechanistic investigation of the Rh-catalyzed cross-coupling reaction between vinylic ethers and aryl Grignard reagents. Kinetic studies reveal first-order and zeroth-order kinetics with respect to the vinyl ether and aryl Grignard reagents, respectively. Computational studies suggest that the reaction proceeds through Mg cation-assisted insertion/anti-beta-oxygen elimination. The results demonstrate the unique chemoselectivity of the Rh-catalyzed reaction.
Article
Chemistry, Physical
Takanori Iwasaki, Wataru Ishiga, Shrinwantu Pal, Kyoko Nozaki, Nobuaki Kambe
Summary: This study reports the mechanistic investigation of the Rh-catalyzed cross-coupling reaction between vinylic ethers and aryl Grignard reagents. The presence of olefinic ligands significantly affects the catalytic activity of Rh precatalysts. Computational studies reveal that the reaction proceeds through Mg cation-assisted insertion/anti-beta-oxygen elimination, with the Mg countercation coordinating to the ethereal oxygen atom in the transition state.
Article
Chemistry, Physical
Shangwei Zhang, Wei Ouyang, Xinghui Xia, Wu Wen, Lorenz Adrian, Gerrit Schueuermann
Summary: Microbial reductive dechlorination is an environmentally friendly and highly desirable method for addressing PCB pollution in soil, sediment, and underground water. The reaction is catalyzed by supernucleophilic cob(i)alamin housed in reductive dehalogenases (RDases), but the mechanism is still unknown.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Multidisciplinary Sciences
Rajesh Kancherla, Krishnamoorthy Muralirajan, Bholanath Maity, Safakath Karuthedath, Gadde Sathish Kumar, Frederic Laquai, Luigi Cavallo, Magnus Rueping
Summary: This paper describes a method for selective alkylation of C(sp(3))-H bonds through triplet sensitization of nickel catalytic intermediates, and provides a detailed elucidation of its reaction mechanism.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Jingjing Li, Yuan Yang, Huimin Di, Jinzhao Wang
Summary: DFT calculations were used to study the mechanism of cascade hydrogenation-cyclization of levulinic acid into gamma-valerolactone catalyzed by half-sandwich iridium complexes. The study revealed that heterolytic hydrogen cleavage, concerted reduction, hydrogen migration, dehydration, and cyclization are key steps in the mechanism. Water acts as a hydrogen donor while counterions act as a hydrogen shuttle in the process. The presence of a double-methoxy group on the bipyridine ligand of the iridium complex increases electron density at the Ir center, leading to enhanced Ir-H bond cleavage.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Engineering, Environmental
Yu Chen, Manav Bhati, Benjamin W. Walls, Bo Wang, Michael S. Wong, Thomas P. Senftle
Summary: This study investigates the photocatalytic oxidation of perfluorocarboxylic acids (PFCA) on hexagonal boron nitride (hBN) and finds that longer-chain PFCAs are more effectively degraded due to stronger adsorption. The researchers also discover that a nitrogen-boron substitutional defect can enhance UVC absorption and PFCA oxidation on hBN.
ENVIRONMENTAL SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Physical
Wenyan Jia, Maoshuai Li, Mingchan Chen, Jing Lv, Mei-Yan Wang, Xiaojun Bao, Xinbin Ma
Summary: In this study, the detailed mechanism pathways for ethylene oxide methoxycarbonylation over Co-based complexes were established, along with the reaction pathway of the main by-product acetaldehyde. The effect of nitrogen-containing heterocycles on the pathways was examined using DFT calculation and experimental study. The addition of pyrazole as a ligand generated the highest conversion and selectively inhibited by-product formation, leading to the highest selectivity of methyl 3-hydroxypropionate.
MOLECULAR CATALYSIS
(2023)
Article
Chemistry, Inorganic & Nuclear
Xiao Yun, Zhangyu Yu, Tao Liu
Summary: The coupling reaction mechanism of 1,6-diyne with benzoquinone catalyzed by a rhodium complex was studied using density functional theory (DFT) calculations. The [2 + 2 + 2] cycloaddition reaction involves four main steps, with olefin insertion being the chemoselectivity-determining step. The effect of different substituents of benzoquinone on the yield was also clarified through the calculations.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Xueying Zhu, Zijiao Chen, Hongqi Ai
Summary: The isomerization mechanism of histidine-containing dipeptide catalyzed by water cluster enhances the activation of N-H and C-H bonds by reducing activation energies and influencing reaction pathways, providing a potential green catalyst option for reactions involving N-H and C-H bond cleavages.
JOURNAL OF MOLECULAR MODELING
(2022)
Article
Chemistry, Organic
Song Liu, Dianmin Zhang, Min Xiao, Chengling Pu, Xiaoqing Zhang, Xiuwen Yang, Tao Zhang, Ruopeng Bai
Summary: C-N bond metathesis is a straightforward and step-economical approach for C-N bond construction. This report presents computational evidence for a new type of reversible reductive elimination/oxidative addition mode in the C-N bond metathesis reaction, which is important for understanding the mechanism of Pd-catalyzed C-N bond formation reactions.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Yuanyuan Li, Jun Zhu
Summary: Density functional theory calculations were used to study the reaction mechanisms of activation of inert carbon-fluorine bonds by nickel catalysts. It was found that the Ni/Mg bimetallic cooperation can cleave the carbon-fluorine bond instead of the traditional oxidative addition, enhancing the selectivity of the KTC cross-coupling.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Qingjun Zhang, Youguang Ma, Aiwu Zeng
Summary: This study investigates the mechanism of palladium-catalyzed carboxylation of thiophene and CO2 using density functional theory (DFT) calculations. The results show that the insertion of CO2 is the rate-determining step for this reaction.
Article
Chemistry, Organic
Antonio Hernandez Daranas, Ariel M. Sarotti
Summary: This report introduces a method that combines quantum mechanical NMR calculations with conformer selection to solve the structure of large, complex, and highly flexible molecules.
Article
Chemistry, Organic
D. Srinivas Reddy, Beduru Srinivas, Kavitha Rachineni, Bharatam Jagadeesh, Ariel M. Sarotti, Debendra K. Mohapatra
Summary: This manuscript describes a convenient, mild, and highly stereoselective method for the allylation of delta-hydroxy-alpha,beta-unsaturated ketones using allyltrimethylsilane mediated by BF3 center dot OEt2, resulting in 2,4-diallyl-2-methyl-6-aryltetrahydro-2H-pyran ring systems with quaternary carbon stereogenic centers. The isolation of TMS-protected lactol as an intermediate strongly supports the proposed mechanistic pathway.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Maria Marta Zanardi, Ariel M. Sarotti
Summary: The study examined the sensitivity of DP4+ when using improper parameter sets, and proposed a customizable methodology for preliminary calculations at any desired level of theory.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Biochemistry & Molecular Biology
Maribel O. Marcarino, Soledad Cicetti, Maria M. Zanardi, Ariel M. Sarotti
Summary: This study discusses the use of DP4+ in the elucidation of natural product structures, highlighting both its strengths and weaknesses, and providing recommendations on how to obtain optimal results. Research shows that DP4+ plays a significant role in resolving disputed natural product structures.
NATURAL PRODUCT REPORTS
(2022)
Article
Chemistry, Organic
Yi-Hsuan Tsai, Milagros Amichetti, Maria Marta Zanardi, Rafael Grimson, Antonio Hernandez Daranas, Ariel M. Sarotti
Summary: A new tool, ML-J-DP4, has been developed for efficiently and accurately determining the most likely structure of complex molecules within minutes using standard computational resources. The tool combines fast Karplus-type J calculations with NMR chemical shifts predictions enhanced with machine learning (ML) in the J-DP4 formalism. The ML predictions provided by this tool are accurate and compare favorably with other ML methods.
Article
Multidisciplinary Sciences
Chunshun Li, Yifei Hu, Xiaohua Wu, Spencer D. Stumpf, Yunci Qi, John M. D'Alessandro, Keshav K. Nepal, Ariel M. Sarotti, Shugeng Cao, Joshua A. V. Blodgett
Summary: Rare actinomycetes are a valuable but underexploited source of bioactive compounds. In this study, a targeted metabologenomic approach was used to identify piperazyl compounds in the rare actinomycete Lentzea flaviverrucosa DSM 44664. The discovery of two dimeric biaryl-cyclohexapeptides, petrichorins A and B, with potent anticancer activity, highlights the potential of rare actinomycetes for drug discovery.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2022)
Article
Chemistry, Organic
Soledad Cicetti, Eugenia Maestre, Rolando A. Spanevello, Ariel M. Sarotti
Summary: A convenient method for the synthesis of highly substituted biomass-derived chiral pyrrolidine via intramolecular click reactions and subsequent functionalization to obtain macrocycles is reported. Extensive DFT study was conducted to understand the origins of experimental difficulties encountered during the macrocyclization stage. The results suggest that the improper conformational landscape of the reactant hinders the pre-organization required for connecting the reactive moieties.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Chunshun Li, Ariel M. Sarotti, Antonio Hernandez Daranas, Xiaohua Wu, Shao-Liang Zheng, Joshua A. V. Blodgett, Shugeng Cao
Summary: The structure of petrichorin C1 (4) derived from petrichorin C (3) has been determined using both NMR spectroscopy and X-ray crystallography. The chemical stability of petrichorins A and C (1 and 3) has been investigated through NMR spectroscopy, X-ray crystallography, and calculations.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Maribel O. Marcarino, Lucas Passaglia, Maria M. Zanardi, Ariel M. Sarotti
Summary: The use of quantum-based NMR methods for the assignment of natural and unnatural product structures has grown. However, the calculation of the conformational landscape of flexible molecules with complex intramolecular H-bonding interactions remains a challenge. The authors present MESSI, a method that improves assignment accuracy by incorporating independent mappings of manipulated ensembles.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Plant Sciences
Bruno A. Franco, Ezequiel R. Luciano, Ariel M. Sarotti, Maria M. Zanardi
Summary: This article introduces an improved DP4+ method by exploring the effect of molecular mechanics architecture on the DP4+ formalism and developing a Python applet to automate the entire process, improving the efficiency and flexibility of structure elucidation.
JOURNAL OF NATURAL PRODUCTS
(2023)
Article
Chemistry, Organic
Ivan Cortes, Ariel M. Sarotti
Summary: This computational study investigates the structure issue of the natural product Dysiherbol A. By evaluating several computational procedures, the researchers provide guidance on what can be done before embarking on complex total synthesis projects.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Ivan Cortes, Ariel M. M. Sarotti
Summary: Oximes and related derivatives featuring a C-N double bond play important roles in various fields of chemistry. Several methods for determining the E/Z configuration have been developed, each with its own advantages and limitations. Among three popular computational methodologies (DP4, DP4+, and ML-J-DP4), DP4+ provides the best confidence but with high computational cost, while ML-J-DP4 shows excellent performance in most cases with less CPU time. A thorough analysis of the structural factors influencing NMR prediction and assignment is also provided.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Marianela G. Pizzio, Zoe B. Cenizo, Luciana Mendez, Ariel M. Sarotti, Ernesto G. Mata
Summary: An efficient and innovative synthetic strategy for generating various carbocyclic moieties through ring closing carbonyl-olefin metathesis is described. The sustainable and attractive protocol utilizes solvent reduction, InCl3 catalyst, and microwave irradiation to achieve high yields (up to 96%) of the target compounds.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Sebastian O. Simonetti, Teodoro S. Kaufman, Rodolfo M. Rasia, Ariel M. Sarotti, Nicolas Grimblat
Summary: By using a combination of DFT and chemometrics in NMR spectra analysis, researchers were able to identify the structure of the main decomposition products of hexamethylenetetramine. This approach also helped propose the structures of similar intermediates and unveil the structure of the main decomposition product of this particular structure.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Faiza Diaba, Gisela Trenchs
Summary: The first violet light-mediated synthesis of gamma- and delta-lactams from N-alkenyl trichloroacetamides is reported in this paper. The reactions are conducted in tetrahydrofuran or 2-methyltetrahydrofuran as the sole solvent without catalysts or additives, under non-anhydrous conditions in an air atmosphere where the solvent serves as the radical initiator.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Feroze Hussain, Sajjad Ahmed, Ashiq Hussain Padder, Qazi Naveed Ahmed
Summary: This study reports a novel and efficient one-pot synthesis method for mixed phosphorotrithioates, which does not require supplementary additives and shows broad applicability.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Hyunjin Oh, Ikyon Kim
Summary: A new 1,2,4-triazole-pyrrolo[1,2-a]pyrazine hybrid system, 6-acylpyrrolo[1,2-a][1,2,4]triazolo[5,1-c]pyrazine, was synthesized using a catalyst-free method. This method involved sequential exposure of pyrrole-2-carbonitrile-derived substrates to DMF-DMA and acyl hydrazide, resulting in the formation of acylated pyrazine and 1,2,4-triazole rings, enabling the installation of various substituents at specific positions on the core skeleton.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Ming Yan, Si-fan Wang, Yong-po Zhang, Jin-zhong Zhao, Zhuo Tang, Guang-xun Li
Summary: Here we developed an efficient photocatalytic approach for the convenient preparation of sulfinamides. The reaction allows for the gram-scale preparation of sulfinamides and the one-pot synthesis of various sulfonyl amides.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Farzaneh Bandehali-Naeini, Zahra Tanbakouchian, Noushin Farajinia-Lehi, Nicolas Mayer, Morteza Shiri, Martin Breugst
Summary: Two tandem catalytic systems were developed for the synthesis of novel 3,4-disubstituted maleimides using the same Ugi adducts. Different maleimide structures can be synthesized using either Pd or Cu catalysis.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Tanya Raghava, Anjan Chattopadhyay, Subhadeep Banerjee, Nivedita Sarkar
Summary: Amine substitution of two ortho fluorine atoms of tetrafluoroterephthalonitrile through SNAr chemistry is easily achievable. But further fluorine substitution is only possible under forcing conditions, yielding valuable fluorophores for bioimaging.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Review
Chemistry, Organic
Anju Chadha, Santosh Kumar Padhi, Selvaraj Stella, Sowmyalakshmi Venkataraman, Thangavelu Saravanan
Summary: Alcohol dehydrogenases are enzymes that use cofactors for oxidation or reduction reactions of alcohols or carbonyl compounds. They are utilized in green chemistry and have applications in the production of pharmaceuticals. Recombinant enzymes have solved the challenge of producing purified enzymes in large quantities. Engineered alcohol dehydrogenases have been used in asymmetric synthesis in industry. Various methods have been established for regenerating expensive cofactors to make the enzymatic process more efficient and economically viable.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)