Article
Chemistry, Physical
Li-Li Han, Ruihao Xia, Xitao Zeng, Zhanwei Li, Yan Qiao, Donghui Wei
Summary: This study provides a comprehensive theoretical investigation into the mechanism and origin of stereoselectivity in biomimetic asymmetric transamination reactions. By uncovering the key steps and energetically advantageous pathways, the origin of stereoselectivity is further predicted. These findings are of great value for understanding and rational design of biomimetic organocatalysts for transamination reactions.
MOLECULAR CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Ming Xiang, Dana E. Pfaffinger, Eliezer Ortiz, Gilmar A. Brito, Michael J. Krische
Summary: The first catalytic enantioselective ruthenium-catalyzed carbonyl reductive couplings of allene pronucleophiles have been described, leading to the formation of enantiomerically enriched diols. Internal chelation directs the intervention of (Z)-sigma-alkoxyallyl-ruthenium isomers, enabling stereospecific carbonyl addition.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Alex Cristofol, Bart Limburg, Arjan W. Kleij
Summary: An efficient Co/organophotoredox dual catalysis protocol has been developed for the stereoselective access to a wide variety of syn-configured 1,3-diols with quaternary carbon centers. Mechanistic control experiments suggest that the stereoselectivity is rationalized via a preferred Zimmerman-Traxler transition state. This newly developed process expands the use of base metal catalysis in constructing challenging quaternary carbon stereocenters.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Simona Zeimyte, Sigitas Stoncius
Summary: The newly synthesized chiral Lewis basic bipyridine N,N'-dioxides exhibited good catalytic activity in asymmetric synthesis reactions, providing high yields of target products, but the enantioselectivity needs improvement.
Article
Chemistry, Organic
Ting-Ting Yang, Congcong Wang, Shi-Jun Li, Min Zhang, Donghui Wei, Yu Lan
Summary: The density functional theory calculations provided insights into the mechanisms and selectivity origins of phosphine-catalyzed [2+3] and [2+4] annulations. The results indicated a preference for allenoate as a C3 synthon under phosphine catalysis, with the catalytic cycle involving eight key processes. Additionally, non-covalent interactions were found to significantly contribute to the stability of the transition state, influencing the chemo- and stereo-selectivities of the reaction.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Yang Wang, Yilu Luo, Miao Zhao, Yan Qiao
Summary: The mechanism and origin of the stereoselectivity in the NHC-catalyzed transformation reaction between an enal and a beta-silyl enone have been systematically investigated. The study reveals that the reaction proceeds through multiple steps including nucleophilic addition, proton shifts, Michael-type addition, and ring closure. The reaction between the enolate intermediate and the beta-silyl enone determines the stereoselectivity, with preference for the RS-configured product due to the higher number of noncovalent intermolecular interactions in the low-energy transition state.
MOLECULAR CATALYSIS
(2023)
Article
Chemistry, Physical
Yang Wang, Han Zhang, Yue Liu, Kaili Gong, Donghui Wei
Summary: In this study, the mechanism of a cobalt-catalyzed hydroacylation reaction between aldehydes and 1,6-enynes and the origin of its stereoselectivity were investigated using the DFT calculational method. The aldehyde-first mechanism was found to be energetically more favorable and the alkene insertion step was identified as the key step determining the stereoselectivity.
MOLECULAR CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Simone Gallarati, Raimon Fabregat, Ruben Laplaza, Sinjini Bhattacharjee, Matthew D. Wodrich, Clemence Corminboeuf
Summary: Hundreds of catalytic methods are developed annually to meet the demand for high-purity chiral compounds, but designing enantioselective organocatalysts remains a challenge. Recent research suggests that combining quantum chemical computations and machine learning can lead to advancements in asymmetric catalysis.
Review
Chemistry, Multidisciplinary
Subhabrata Dutta, Trisha Bhattacharya, Daniel B. Werz, Debabrata Maiti
Summary: Allylation reactions, pioneered by Tsuji and Trost, are essential C-C bond-forming transformations with broad applications in synthetic chemistry, bioactive compounds, and pharmaceutical industries. The development of synthetic strategies and the emergence of site-selective C-H activation have further expanded the scope of allylation reactions, eliminating the need for pre-functionalized substrates and activated allylating reagents.
Article
Biochemistry & Molecular Biology
Qaim Ali, Yongyong Chen, Ruixue Zhang, Zhewei Li, Yanhui Tang, Min Pu, Ming Lei
Summary: The reaction mechanism and origin of stereoselectivity in the asymmetric hydrogenation of oximes catalyzed by chiral iridium complexes have been revealed using DFT calculations. The involvement of methanesulfonate anion was found to be crucial in determining the chirality of the reaction, and its absence resulted in higher energy barriers for the hydride transfer step. The non-covalent interactions between the substrate, anion, and catalyst played a significant role in stabilizing the catalytic species and influencing the stereoselectivity of the reaction.
Article
Multidisciplinary Sciences
Lei Wang, Chuiyi Lin, Qinglei Chong, Zhihan Zhang, Fanke Meng
Summary: Catalytic enantioselective introduction of a propargyl group is an important carbon-carbon forming reaction, but only a few Cu- or Ni-catalyzed protocols with limited reaction modes are known. Here, the authors describe a photoredox/cobalt-catalyzed propargyl addition to aldehydes via propargyl radicals which enables the construction of a broad scope of homopropargyl alcohols that are otherwise difficult to access. Mechanistic studies and DFT calculations provide evidence for the involvement of propargyl radicals, the origin of the stereoconvergent process, and the stereochemical models.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Marie Vayer, Sophie Rodrigues, Solene Miaskiewicz, David Gatineau, Yves Gimbert, Vincent Gandon, Christophe Bour
Summary: This study describes a gallium-catalyzed C-H propargylation of electron-rich arenes using bromoallenes. By using K2CO3 as a base, the side hydroarylation process catalyzed by adventitious protons from the solvent can be bypassed, and the GaCl3/K2CO3 system is found to trigger a wide range of reactions.
Article
Chemistry, Organic
Hui-Qing Yang, Ya-Ning Hou, Jing-Yun Chen, Sheng-Qiang Guo, Hui-Xian Yang, Xin Wang
Summary: We investigated the mechanism of asymmetric reductive carboxylation of N-(2-bromophenyl)-N-methylmethacrylamide catalyzed by a nickel complex using DFT calculations. The reaction proceeds via a multistep and elaborate mechanism, with CO2 showing a preference for inserting into the Ni(I) intermediate.
TETRAHEDRON LETTERS
(2023)
Article
Biochemistry & Molecular Biology
Angela Patti, Claudia Sanfilippo
Summary: The catalytic promiscuity of lipases has gained increasing interest as a tool for expanding their application in organic synthesis. However, the production of enantiopure products through lipase catalysis is still a challenge.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2022)
Article
Chemistry, Organic
Nicolo Tampellini, Paolo Righi, Giorgio Bencivenni
Summary: A computational study using density functional theory was conducted to understand the mechanism of atroposelective desymmetrization of N-(2-t-butylaryl)maleimide catalyzed by 9-amino(9-deoxy) epi-quinine. The results showed that the atroposelectivity was achieved through steric and dispersion interactions of the catalyst. The crucial role of N-Boc-L-Ph-glycine was identified in forming a closed transition-state geometry and activating the reaction partners.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Medicinal
Jill F. Ellenbarger, Inna Krieger, Hsiao-ling Huang, Silvia Gomez-Coca, Thomas R. Ioerger, James C. Sacchettini, Steven E. Wheeler, Kim R. Dunbar
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2018)
Article
Chemistry, Physical
Yanfei Guan, Victoria M. Ingman, Benjamin J. Rooks, Steven E. Wheeler
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2018)
Article
Chemistry, Organic
Tia L. Walker, Ian S. Taschner, Sharath M. Chandra, Michael J. Taschner, James T. Engle, Briana R. Schrage, Christopher J. Ziegler, Xinfeng Gao, Steven E. Wheeler
JOURNAL OF ORGANIC CHEMISTRY
(2018)
Article
Chemistry, Multidisciplinary
Rajat Maji, Heena Ugale, Steven E. Wheeler
CHEMISTRY-A EUROPEAN JOURNAL
(2019)
Article
Chemistry, Medicinal
Andrea N. Bootsma, Steven E. Wheeler
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2019)
Article
Chemistry, Physical
Drew P. Harding, Andrea N. Bootsma, Steven E. Wheeler
JOURNAL OF PHYSICAL CHEMISTRY B
(2019)
Article
Chemistry, Medicinal
Andrea N. Bootsma, Steven E. Wheeler
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2019)
Article
Chemistry, Multidisciplinary
Andrea N. Bootsma, Analise C. Doney, Steven E. Wheeler
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Chemistry, Multidisciplinary
Drew P. Harding, Laura J. Kingsley, Glen Spraggon, Steven E. Wheeler
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Victoria M. Ingman, Anthony J. Schaefer, Laura R. Andreola, Steven E. Wheeler
Summary: With the advancement of computational quantum chemistry tools, larger and more complex molecular systems can now be studied. However, the analysis of these systems requires a large number of computations, making manual processes tedious and error-prone. To address this issue, a suite of free, open-source tools has been developed to automate quantum chemistry workflows.
WILEY INTERDISCIPLINARY REVIEWS-COMPUTATIONAL MOLECULAR SCIENCE
(2021)
Article
Chemistry, Multidisciplinary
Anthony J. Schaefer, Victoria M. Ingman, Steven E. Wheeler
Summary: The SEQCROW bundle for UCSF ChimeraX offers advanced structure editing capabilities and quantum chemistry utilities specifically designed for complex organic and organometallic compounds. Users can efficiently generate publication-quality molecular structure figures, visualize vibrational modes, compute molecular descriptors, and manage computational tasks with this plugin.
JOURNAL OF COMPUTATIONAL CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Rajat Maji, Sharath Chandra Mallojjala, Steven E. Wheeler
Summary: This article introduces the importance of electrostatic interactions in catalytic systems and the application of computational chemistry methods in studying these interactions. The author reveals the role of electrostatic interactions in reaction mechanisms and selectivity through quantum chemical computations, using asymmetric organocatalysis as specific examples.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Materials Science, Multidisciplinary
William J. Mullin, Peter Mueller, Anthony J. Schaefer, Elisa Guzman, Steven E. Wheeler, Samuel W. Thomas
Summary: This study investigates the stacking interactions between aromatic rings and heterocycles, revealing that fluorinated side-chains and electron-rich units have interactions in the solid state, while electron-deficient units are incompatible. These interactions play a significant role in compound stability.
JOURNAL OF MATERIALS CHEMISTRY C
(2022)
Article
Chemistry, Organic
Laura R. Andreola, Steven E. Wheeler
Summary: Automated transition state structure computations have revealed unexpected conformations of the key stereodifferentiating benzyl group in a recently reported Pd-catalysed conjugated addition reaction. The stereoselectivity of this reaction is determined by favorable non-covalent contacts between the benzyl group and the substrates, as well as torsional strain in the primary transition state structure.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Ian S. Taschner, Tia L. Walker, Sharath M. Chandra, Briana R. Schrage, Christopher J. Ziegler, Xinfeng Gao, Steven E. Wheeler
ORGANIC CHEMISTRY FRONTIERS
(2020)
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)