Article
Chemistry, Organic
Linlong Dai, Qiaohong Zhu, Jie Zeng, Yuheng Liu, Guofu Zhong, Xiaoyu Han, Xiaofei Zeng
Summary: The study presents an effective strategy for the synthesis of chiral imidazolidines through catalytic reactions, achieving high yields and enantioselectivities. Additionally, this method can also be applied in the synthesis of chiral vicinal diamines by adjusting the reaction conditions.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Haruna Araki, Shohei Furuya, Kazuya Kanemoto, Shin-ichi Fukuzawa
Summary: The conjugated addition reaction of 1-pyrroline-5-carbonitrile to alpha-enones was effectively catalyzed by AgF/ThioClickFerrophos (TCF) in diethyl ether in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and nearly single diastereomers of adducts with good enantiomeric excesses (up to 97% ee) were obtained in high yields. The reduction of the nitrile group with H2/Raney Ni in ethanol successfully transformed the conjugate adduct to the corresponding spirocyclic piperidine (60% yield) as a single stereoisomer.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Houda Gazzeh, Fadwa Rouatbi, Sami Chniti, Moheddine Askri, Michael Knorr, Carsten Strohmann, Christopher Golz, Al Mokhtar Lamsabhi
Summary: The mechanism of a three-component one-pot cycloaddition reaction was studied using both theoretical and experimental methods. The reactivity difference between the unsymmetrical exocyclic dienones was analyzed to explain the observed regio- and stereoselectivity, and the results were confirmed by calculations. The reaction proceeded under kinetic control and showed chemoselectivity, producing two highly diastereomerically enriched compounds. The intermolecular hydrogen bonding and optical properties of the products were also investigated.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Organic
Mamta Gill, Arko Das, Vinod K. Singh
Summary: An enantioselective (3+2) cycloaddition reaction has been reported for the synthesis of chiral polysubstituted pyrrolidines. The reaction displays opposite regioselectivity with excellent enantioselectivities and yields. Interestingly, changing the alpha-substituents of the iminoesters results in the formation of normal (3+2) cycloaddition products with excellent enantioselectivities as well.
Article
Chemistry, Organic
Jose Cortes Vazquez, Jacqkis Davis, Vladimir N. Nesterov, Hong Wang, Weiwei Luo
Summary: A formal [3 + 3] cyclization reaction has been developed for the synthesis of 1,3,4-oxadiazinanes with generally high yields (up to 96%). The reaction, catalyzed by Sc(OTf)(3), has a broad substrate scope for both diaziridines and quinones. The synergistic activation of 1,3-dipolar diaziridines and dipolar quinones was found to be essential for enabling this reaction.
Article
Chemistry, Organic
Zhenjie Gan, Ke Li, Hui Zhang, Er-Qing Li
Summary: A highly efficient copper/GanPhos-catalyzed 1,3-dipolar cycloaddition of azomethine ylides is reported in this study, providing optically active spiro[dihydronaphthalene-2,3'-pyrrolidine]s with one spiro quaternary and three tertiary stereogenic centers in good yields and high ee values. This protocol demonstrates high diastereo- and enantioselectivity, broad substrate scope, and mild reaction conditions.
SYNTHESIS-STUTTGART
(2021)
Article
Biochemistry & Molecular Biology
Eduardo Garcia-Minguens, Marcos Ferrandiz-Saperas, M. de Gracia Retamosa, Carmen Najera, Miguel Yus, Jose M. Sansano
Summary: This study investigated the enantioselective 1,3-dipolar cycloaddition between (Z)-nitroalkenes bearing a masked amino group in the beta-position and imino esters, using various chiral ligands and silver salts. The absolute configuration of the reaction products was determined through NMR experiments and electronic circular dichroism (ECD), leading to the generation of the corresponding cis-2,3-diaminoprolinate in excellent enantiomeric ratio.
Article
Chemistry, Applied
Kai-Kai Wang, Yan-Li Li, Rong-Xiang Chen, Ai-Li Sun, Zhan-Yong Wang, Ying-Chao Zhao, Ming-Yue Wang, Shi Sheng
Summary: The additive-free 1,3-dipolar cycloaddition reaction enables diversity-oriented synthesis of novel and structurally complex derivatives in high yields and excellent diastereoselectivities.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Shohei Furuya, Kenji Muroi, Kazuya Kanemoto, Shin-ichi Fukuzawa
Summary: The stereodivergent asymmetric synthesis of 2,5-trans/cis pyrrolidines by 1,3-dipolar cycloaddition using two different types of activated alkenes is described. The reaction using ylidene-isoxazolones as dipolarophiles produced 2,5-trans pyrrolidines, while the reaction using acyclic enones as activated alkenes afforded 2,5-cis substituted pyrrolidines.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Multidisciplinary
Mahzad Dehghany, Jennifer M. Schomaker
Summary: Silver offers a cost-effective alternative for asymmetric transformations of alkenes and alkynes, driving selectivity through non-covalent interactions. The reactions enable direct enantioselective transformations of the alkene/alkyne pi bond and functionalization at adjacent C-H bonds.
CURRENT OPINION IN GREEN AND SUSTAINABLE CHEMISTRY
(2021)
Article
Chemistry, Organic
Yabo Deng, Zhenghao Dong, Fengyun Gao, Yifei Guo, Mengmeng Sun, Yongzhen Li, Yalan Wang, Qushuo Chen, Kairong Wang, Wenjin Yan
Summary: An amino-controlled regiodivergent asymmetric synthesis of CF3-containing spiro-pyrrolidine-pyrazolone compounds is described, offering adducts in excellent yields, dr, and ee when using alkaloid-derived squaramide as the catalyst. Switching to cyclohexanediamine-derived squaramide led to the formation of a series of structural isomers through a switched umpolung reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yi-Nan Li, Xin Chang, Qi Xiong, Xiu-Qin Dong, Chun-Jiang Wang
Summary: The Cu-catalyzed endo-selective asymmetric 1,3-dipolar cycloaddition of azomethine ylides with ethenesulfonyl fluorides (ESFs) provides an efficient method to access a wide range of chiral pyrrolidine-3-sulfonyl fluorides and other chiral sulfonyl derivatives with good yields and stereoselectivity, demonstrating their synthetic utility in SuFEx chemistry.
CHINESE CHEMICAL LETTERS
(2021)
Article
Chemistry, Organic
You-Gui Li, Wei-Ke Chen, You-Qiang Guo, Zhang Zhu, Jing-Jing Cao, Zhen-Yu Wang, Xiang Wu
Summary: A new method for synthesizing hexahydropyrrolo-isoquinolines through 1,3-dipolar cycloaddition is described. This method involves the reaction of cinnamaldehydes with azomethine ylides generated from cinnamaldehydes and tetrahydroisoquinolines. The key features of this method are easily available substrates, good functional group tolerance, and mild reaction conditions. The relative configurations of the products are confirmed by X-ray analysis, and a plausible mechanism is proposed. A gram-scale experiment and some chemical transformations were conducted to demonstrate the synthetic utility of this approach. (c) 2023 Elsevier Ltd. All rights reserved.
TETRAHEDRON LETTERS
(2023)
Article
Chemistry, Organic
Zhigang Chen, Wei Zhong, Sihua Liu, Ting Zou, Kaiqiang Zhang, Chuliang Gong, Wenyan Guo, Feizhi Kong, Libo Nie, Shunqin Hu, Haifei Wang
Summary: In this study, we report the highly diastereo- and enantioselective [3 + 2] cycloadditions of iminoesters with various alpha-substituted acrylates. The reactions are catalyzed by AgHMDS/DTBM-Segphos or Ag2O/CA-AA-Amidphos, and result in the stereodivergent synthesis of chiral C4-ester-quaternary exo- or endo-pyrrolidines with high yields and excellent diastereo- and enantioselectivities (up to >99:1 dr and >99% ee). The gram-scale synthetic exo-adduct is particularly significant, as it enables the total synthesis of the spirotryprostatin A alkaloid in nine steps with a 36% overall yield.
Article
Biochemistry & Molecular Biology
Alexei N. Izmest'ev, Valentina A. Karnoukhova, Alexander A. Larin, Angelina N. Kravchenko, Leonid L. Fershtat, Galina A. Gazieva
Summary: This study proposes methods for the synthesis of two types of isomeric dispirocompounds based on imidazothiazolotriazine and pyrrolidineoxindole. The first method involves a 1,3-dipolar cycloaddition and column chromatography to obtain a mixture of isomers. The second method involves rearrangement to obtain the other isomer.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2022)
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, Inorganic & Nuclear
Gregory F. Grawe, Katia M. Oliveira, Celisnolia M. Leite, Tamires D. de Oliveira, Joao Honorato, Antonio G. Ferreira, Eduardo E. Castellano, Marcia R. Cominetti, Rodrigo S. Correa, Alzir A. Batista
Summary: Three new ruthenium(ii) diphosphine complexes containing an acylthiourea ligand were synthesized and characterized, showing cytotoxicity against lung cancer cell lines. These complexes can act as cytotoxic agents for lung cancer treatment.
DALTON TRANSACTIONS
(2022)
Article
Biochemistry & Molecular Biology
Nicolas Veiga, Natalia Alvarez, Eduardo E. Castellano, Javier Ellena, Gianella Facchin, Maria H. Torre
Summary: The study investigated a series of copper complexes with amino acids and dipeptides, as well as their performance in antitumor mechanisms. Results indicate that Cu-amino acid complexes are strong producers of reactive oxygen species, while Cu-dipeptide-phen complexes are good SOD mimics.
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
Geeta Devi Yadav, Pooja Chaudhary, Balaram Pani, Surendra Singh
Summary: Chiral transition metal complexes with privileged ligands are efficient catalysts for various asymmetric organic transformations. Transition metal complexes of C1-symmetric pyrrolidine-based ligands have been widely used in asymmetric organic reactions. However, a comprehensive review article on the transition metal complexes of chiral C1-symmetric pyrrolidine-based ligands derived from (L)-proline has not been published.
TETRAHEDRON LETTERS
(2024)
