Article
Chemistry, Organic
Gregg A. Barcan, Doo-Hyun Kwon, Jiasheng Guo, John A. Kowalski, Li Liu, Mark Nilson, Jack Sisko, Huan Wang, Timothy A. Brown, Habib Gholipour-Ranjbar
Summary: Establishing the two stereocenters in the benzothiaze-pine ring of linerixibat (GSK2330672) has always been a long-standing problem at GSK. Our solution is based on an episulfonium-controlled Ritter reaction followed by a sulfoxide-directed reduction. Both steps are supported by literature precedent and computational experiments. Transition state modeling suggests that the sulfoxide-directed reduction proceeds through electronic repulsion between the lone pair of electrons on sulfur and the incoming borohydride anion.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Ramon de la Serna, Joaquin Perez-Pariente, Luis Gomez-Hortigueela
Summary: In this study, the asymmetric catalytic activity of GTM-3 chiral zeolite in the ring-opening reaction of trans-stilbene oxide using alcohols as nucleophiles was systematically explored. The results showed that a proper chiral host-guest size match is crucial for the chiral manifestation of the zeolite catalyst. Additionally, secondary alcohols with larger size exhibited higher enantioselectivity than their linear counterparts. Furthermore, variation of reaction conditions, such as the concentration of the epoxide and reaction temperature, could greatly influence the enantioselectivity and selectivity of the reaction.
Article
Chemistry, Multidisciplinary
Peng-Ying Jiang, San Wu, Guan-Jun Wang, Shao-Hua Xiang, Bin Tan
Summary: QUINAPs have been widely used in enantioselective transformations, but their limited substrate range and high cost hinder their broader application. In this study, we report the first atroposelective oxidation of an N atom using a chiral ketone catalyst, allowing the kinetic resolution of QUINAPOs with excellent enantioselectivity. The enantioenriched products can be easily converted into the desired QUINAP targets without loss of stereochemical integrity. Mechanistic investigations reveal the involvement of a dioxirane as the active catalytic species.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Peng-Ying Jiang, San Wu, Guan-Jun Wang, Shao-Hua Xiang, Bin Tan
Summary: QUINAPs are a crucial class of chiral compounds that have remarkable features in stereoinduction. However, their restricted substrate range and expensive price limit their broader utilization. In this study, the first atroposelective oxidation of an N atom using a chiral ketone catalyst was described, allowing the kinetic resolution of QUINAPOs with excellent enantioselectivity. Mechanistic investigations revealed the role of a dioxirane as the active catalytic species. The developed protocol has practicality and can be applied in enantioselective transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Josep Mas-Rosello, Ana G. Herraiz, Benoit Audic, Aragorn Laverny, Nicolai Cramer
Summary: The development of new chiral ligands is crucial for stereocontrol in metal-catalyzed reactions, especially with the increasing demand for bioactive molecules as single enantiomers. The successful application of Cp-X ligands in metal-catalyzed transformations allows access to valuable chiral molecules, with critical comparisons of existing ligand families and discussion of future research directions for further enhancing their performance and application in enantioselective catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Won Jun Jang, Jeongkyu Woo, Jaesook Yun
Summary: The study reported a method to synthesize enantioenriched alkylboron compounds through conjugate addition, which are influenced by two contiguous carbon stereogenic centers, with high yield and enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Gao-feng Yang, Yi Yuan, Yin Tian, Shi-qi Zhang, Xin Cui, Bing Xia, Guang-xun Li, Zhuo Tang
Summary: Desymmetrizing enantioselective hydrolysis of in situ-generated symmetric aza-dichlorosulfonium from sulfenamides allows for the preparation of chiral sulfonimidoyl chlorides, which serve as a general stable synthon for obtaining a series of chiral S(VI) derivatives.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Shiyu Xiang, Taotao Lu, Junjun Liu, Qingyang Zhao
Summary: An unprecedented redox transformation of β-sulfinyl esters to generate sulfinate anions has been discovered, enabling the asymmetric sulfonylation of vinylidene o-quinone methides and providing various sulfone-based axially chiral styrenes with excellent enantioselectivities.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Tomoyuki Yanagi, Takayuki Tanaka, Hideki Yorimitsu
Summary: A series of dihetero[8]helicenes have been systematically synthesized in enantiomerically enriched forms using the characteristic transformations of the organosulfur functionality. The study highlights the effect of endocyclic atoms on the structures and optical properties of these compounds, as well as the unexpected conformational stability of the common helical framework, achieved through efficient systematic synthesis and comprehensive evaluation of physical properties.
Article
Chemistry, Multidisciplinary
Zhibin Guo, Daehyun Oh, Min Sagong, Jewon Yang, Geumwoo Lee, Hyeung-geun Park
Summary: An efficient method for synthesizing chiral malonates was established using enantioselective phase transfer catalysis. The a-alkylation reaction of 2,2-diphenylethyl tert-butyl a-methylmalonates with (S,S)-3,4,5-trifluorophenyl-NAS bromide as a phase-transfer catalyst successfully yielded corresponding a-methyl-a-alkylmalonates. These compounds are versatile chiral building blocks with a quaternary carbon center, obtained in high chemical yields (up to 99%) and excellent enantioselectivities (up to 98% ee). Selective hydrolysis of a,a-dialkylmalonates to the corresponding chiral malonic monoacids was achieved using basic (KOH/MeOH) and acidic conditions (TFA/CH2Cl2), demonstrating the practicality of the method.
FRONTIERS IN CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Yan-Bo Li, Hu Tian, Shuai Zhang, Jun-Zhao Xiao, Liang Yin
Summary: In this study, a copper(I)-catalyzed reaction of diarylphosphines and O-benzoyl hydroxylamines was developed, leading to the synthesis of aminophosphinites and P-chiral aminophosphinites. The reaction mechanism was proposed and further transformation to P-chiral phosphines was achieved.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Li Ling, Zeli Song, He Shan, Chao Wang, Shouting Li, Yanjiao Wang, Jianfeng Hu, Qian Chen, Hao Zhang, Yong Yang
Summary: A series of planar chiral indene-fused ferrocenes were successfully synthesized with excellent yields (up to 99%) and high enantioselectivities (up to 99% ee) through intramolecular asymmetric C-H arylation. These compounds were then transformed to chiral ferrocenyl phosphines, featuring both planar and central chiralities, in good yields (up to 83%) and excellent diastereoselectivities (up to 99% de) through diastereoselective phosphination. The newly developed ligands demonstrated potential applications in a Pd-catalyzed enantioselective allylic alkylation reaction with high enantioselectivity (92% ee) and good yield (89%).
CHEMICAL COMMUNICATIONS
(2023)
Review
Chemistry, Applied
Giovanni Maria Fusi, Silvia Gazzola, Umberto Piarulli
Summary: Transition metal chiral catalysts can have metal stereocenters in different coordination geometries, with stability achieved through the use of multidentate ligands or cyclopentadienyl anions to prevent decomplexation and recomplexation of labile ligands, allowing for highly enantioselective reactions.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Yoshiaki Maeda, Suguru Hamada, Yusuke Aota, Kazuya Otsubo, Taichi Kano, Keiji Maruoka
Summary: In this study, we demonstrated an asymmetric synthesis of chiral sulfoximines through a stereospecific S-alkylation of readily accessible chiral sulfinamides under practical conditions. The identification of the intermediate structure in our previously reported S-alkylation by X-ray crystallographic analysis was crucial to establish the practical conditions.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Na Shao, Valerie Monnier, Laurence Charles, Jean Rodriguez, Cyril Bressy, Adrien Quintard
Summary: This study reports a multicatalytic strategy for the synthesis of a new type of scaffold containing a tetrasubstituted stereocenter embedded in fluorohydrin motifs. The method involves organocatalyzed fluorination and diastereoselective aldol reaction, resulting in the stereoselective synthesis of fluorinated 1,3-diols.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Alessio Cimmino, Fabrizio Freda, Ernesto Santoro, Stefano Superchi, Antonio Evidente, Massimo Cristofaro, Marco Masi
Summary: The organic extract of Dittrichia viscosa showed significant acaricidal activity against Varroa destructor, with alpha-costic acid being identified as a toxic compound for the parasite mite. This suggests a potential use of alpha-costic acid to control Varroa mites without any harmful effects on honey bees. Additionally, the absolute configuration of alpha-costic acid could be reliably determined through DFT computational analysis of chiroptical spectra.
NATURAL PRODUCT RESEARCH
(2021)
Article
Biochemistry & Molecular Biology
Giulia Marsico, Umberto Calice, Patrizia Scafato, Sandra Belviso, Antonio Evidente, Stefano Superchi
Summary: This study compares the computational analysis of electronic circular dichroism (ECD) spectra and the application of biphenyl chiroptical probes in the absolute configuration assignment. The results highlight the usefulness of biphenyl probes in the determination of conformationally mobile and ECD silent compounds, which cannot be handled by computational analysis methods.
Article
Biochemistry & Molecular Biology
Assunta Summa, Patrizia Scafato, Sandra Belviso, Guglielmo Monaco, Riccardo Zanasi, Giovanna Longhi, Sergio Abbate, Stefano Superchi
Summary: A novel alpha-tetrazole-substituted 1,1'-binaphthylazepine chiral catalyst has been synthesized and its absolute configuration has been determined using DFT computational analysis of the VCD spectrum. The catalyst showed low enantioselectivity in the synthesis of chiral flavanones.
Article
Food Science & Technology
Veronique Mathieu, Stefano Superchi, Marco Masi, Patrizia Scafato, Alexander Kornienko, Antonio Evidente
Summary: Natural compounds have long been an important source for discovering new drugs, but no fungal metabolite has been marketed as an anticancer drug. In this study, the researchers evaluated the anticancer activity of metabolites produced by three phytopathogenic fungi. One of the metabolites, Radicinin, showed significant anticancer activity against cancer cells. The study also explored the potential application of Radicinin analogues as anticancer agents.
Article
Biochemistry & Molecular Biology
Marco Masi, Roberta Di Lecce, Umberto Calice, Benedetto Teodoro Linaldeddu, Lucia Maddau, Stefano Superchi, Antonio Evidente
Summary: An undescribed disubstituted dihydrofuranone, named diplofuranoxin, was isolated from the fungal species Diplodia subglobosa, along with six known metabolites. The metabolites were screened for biological activities, and two of them showed activity in the bioassays.
Article
Biochemistry & Molecular Biology
Anna Santarsiero, Ilaria Pappalardo, Gabriella Margherita Rosa, Isabella Pisano, Stefano Superchi, Paolo Convertini, Simona Todisco, Patrizia Scafato, Vittoria Infantino
Summary: Hepatocellular carcinoma (HCC) is the most common type of liver cancer and a significant cause of cancer-related deaths. In this study, a newly synthesized chalcone ETTC showed cytotoxic activity and induced apoptosis in HCC cells through the activation of the intrinsic pathway of apoptosis and mitochondrial targeting. These findings suggest the potential antitumor effect of ETTC in HCC.
Article
Chemistry, Organic
Roberto Bisaccia, Patrizia Scafato, Daniele Casarini, Stefano Superchi
Summary: 5,5,7,7-Tetrametyl-6,7-dihydro-5H-dibenzo[c,e]azepine has been synthesized as a possible pro-chiral unit for chiral catalyst construction and as a molecular chirality sensor for absolute configuration assignment. A straightforward synthetic strategy for its preparation was described, and the torsional flexibility of the aryl-aryl bond was determined using VT-NMR study, making it suitable for both chirality probe and tropos moiety in chiral ligands.
Article
Biochemistry & Molecular Biology
Simone Samperna, Clarissa Zanotti, Patrizia Scafato, Angela Boari, Sabina Visconti, Maurizio Vurro, Stefano Superchi, Antonio Evidente, Mauro Marra
Summary: Radicinin is a phytotoxic compound isolated from the culture filtrates of the phytopathogenic fungus Cochliobolus australiensis. It has potential as a natural herbicide. Using tomato as a model plant, it was found that (+/-)-3-deoxyradicinin induced chlorosis, ion leakage, hydrogen peroxide production, membrane lipid peroxidation, and uncontrolled opening of stomata, leading to plant wilting. The compound targeted chloroplasts, causing an overproduction of reactive singlet oxygen species and activating genes related to chloroplast-specific programmed cell death.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Multidisciplinary
Francesco Pizzoli, Alessandro Mita, Fabrizio Caroleo, Sara Nardis, Umberto Calice, Marilena Caporale, Sandra Belviso, Stefano Superchi, Alessia Marconi, Matteo Calvaresi, Chiara Capolungo, Luca Prodi, Kevin M. Smith, Frank R. Fronczek, Roberto Paolesse
Summary: This study explores the method of obtaining dianionic corrole ligands through alkylation of one of the inner-core nitrogen atoms, and discusses the structural characteristics of the reaction products and their application in coordination chemistry and biological systems.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
