Review
Chemistry, Multidisciplinary
Yichen Wu, Peng Wang
Summary: Optically active organosilanes have been demonstrated to be versatile chiral reagents in synthetic chemistry. Monohydrosilanes, which bear a Si-H bond, are especially unique due to their facile transformations through stereospecific bond-formation reactions. In addition, they have also been used as chiral reagents for alcohol resolution, chiral auxiliaries, mechanistic probes, and potential optoelectronic materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Kanak Kanti Das, Somenath Mahato, Subrata Hazra, Santanu Panda
Summary: Organoboron compounds are important and versatile synthetic intermediates in the preparation of organic molecules. Among all organoboron compounds, beta-boryl carbonyl compounds have emerged as promising intermediates for various synthetic transformations. This mini-review provides an overview of the numerous racemic and asymmetric beta-borylation methods developed to date.
Review
Chemistry, Applied
Seoung-Mi Choi, Ju Hyun Kim
Summary: This review summarizes the progress made in the synthesis of 2H-pyrroles since 2000, including methods such as dearomatization of 1H-pyrrole, oxidation of pyrrolines or pyrrolidines, ring construction via catalytic cycloaddition, and rearrangement of 3H-pyrroles.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Review
Chemistry, Multidisciplinary
Hsuan-Hung Liao, Shinje Minoza, Shao-Chi Lee, Magnus Rueping
Summary: This review presents the progress of aza-ortho-quinone methide (aza-o-QM) chemistry in the past few decades. Various catalytic strategies using transition metals and organocatalysts are discussed for controlling aza-o-QM intermediates, leading to the synthesis of complex molecular scaffolds.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Wenbo Ming, Xiaocui Liu, Lujia Mao, Xiao Gu, Qing Ye
Summary: This review article summarizes recent advances in transition-metal catalyzed preparation of chiral allylboronates, focusing on developments within the past three years and emphasizing asymmetric catalysis. The discussion is divided into substrate-controlled and catalyst-controlled synthesis based on mechanisms for achieving selectivity in terms of chemo-, regio-, stereo- and enantioselectivities.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yinliang Guo, Jia-Tian Lu, Runting Fang, Yang Jiao, Jiaqi Liu, Tuoping Luo
Summary: Veratrum alkaloids are highly complex steroidal alkaloids with intricate structural and stereochemical features, exhibiting diverse pharmacological activities. A new synthetic pathway has been developed to access this natural product family, leading to the first total synthesis of (-)-zygadenine. Key steps in this synthetic route include a stereoselective intramolecular Diels-Alder reaction and a radical cyclization, followed by a meticulously designed sequence of redox manipulations to achieve the de novo synthesis of this highly oxidized Veratrum alkaloid.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Multidisciplinary
Dzmitry Kananovich, Gabor Zoltan Elek, Margus Lopp, Victor Borovkov
Summary: Despite significant progress in asymmetric catalytic oxidations, developing sustainable and environmentally friendly enantioselective oxidation techniques remains a challenge. Molecular oxygen as the sole oxidant offers advantages due to its availability, cost-effectiveness, and environmental friendliness, and recent research has focused on utilizing it in catalytic enantioselective oxidations.
FRONTIERS IN CHEMISTRY
(2021)
Review
Multidisciplinary Sciences
Chiara Costabile, Stefania Pragliola, Fabia Grisi
Summary: The last decades have witnessed the rapid growth of applications of N-heterocyclic carbenes (NHCs) in various chemistry fields. Due to their unique properties, NHCs have become a powerful tool in coordination chemistry, particularly in the synthesis of stable metal-ligand frameworks with main group metals and transition metals. This article provides an overview of the use of five-membered monodentate C-2-symmetric N-heterocyclic carbenes (NHCs) as ligands for transition-metal complexes and highlights their most relevant applications in asymmetric catalysis.
Article
Nanoscience & Nanotechnology
Muhammad Saqib, Phong A. Tran, Batur Ercan, E. Yegan Erdem
Summary: Janus particles have asymmetrical nature which make them superior to conventional particles. Microfluidic-based techniques are popular for their versatility and control over reaction conditions, leading to complex functionalities being imparted to the Janus particles.
INTERNATIONAL JOURNAL OF NANOMEDICINE
(2022)
Review
Chemistry, Applied
Helene Pellissier
Summary: This review provides an update on the field of enantioselective domino reactions catalyzed by chiral catalysts derived from noble metals, such as palladium, silver, rhodium, ruthenium, iridium, and gold, since the beginning of 2019. It showcases the diverse range of these catalysts, enabling unprecedented asymmetric domino reactions with excellent enantioselectivity and providing access to a wide variety of complex chiral molecules.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Inorganic & Nuclear
Yali Lv, Mengxiang Ren, Ping Wang, Zupeng Chen, Xiaoling Mou, Jiahui Fan, Jun Zhang, Ronghe Lin, Jingwei Li, Yunjie Ding
Summary: A novel synthetic strategy for fabricating nickel-based bimetallic interstitial compounds with the formula MNi3Cx (M = Zn, In, Ga) is developed based on a simple solid-state transformation. The resulting compounds have a single-phase structure and are covered with N-doped carbon shells. This strategy provides a promising scaffold for the fabrication of advanced multi-metallic interstitial compounds.
DALTON TRANSACTIONS
(2023)
Review
Chemistry, Applied
Helene Pellissier
Summary: This review updates the research in the field of enantioselective domino reactions promoted by chiral catalysts derived from first row metals, such as zinc, iron, copper, scandium, nickel, cobalt, titanium, chromium and magnesium, since the beginning of 2019. It illustrates the impressive range of novel highly enantioselective domino reactions that can be achieved with a diversity of these catalysts, providing a one-pot access to very complex and functionalized chiral molecules from simple starting materials.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Zhiyuan Qian, Yukun Cheng, Shunan Zhao, Keith Man-Chung Wong
Summary: A new bipyridine fused rhodamine-like chelating ligand and its corresponding transition metal complexes of platinum(II) and iridium(III) were designed, synthesized, and structurally characterized. These complexes exhibit unique photophysical properties and undergo spirocarbon ring-opening properties in the presence of acid or metal ions. The platinum(II) complex shows dissociation with Hg2+ ions, while the emission titration studies of iridium(III) complexes are affected by the quenching process from the ring-opened form of ligand's lower-lying non-emissive excited state.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Biochemistry & Molecular Biology
Ana R. Gomes, Ana S. Pires, Ana M. Abrantes, Ana C. Goncalves, Saul C. Costa, Carla L. Varela, Elisiario T. Silva, Maria F. Botelho, Fernanda M. F. Roleira
Summary: Steroidal oxime compounds were synthesized and evaluated for their cytotoxicity in multiple cancer cell lines, with (17E)-5 alpha-androst-3-en-17-one oxime (3,4 - OLOX) showing the most promising results in decreasing tumor cell proliferation. These compounds may serve as a starting point for the discovery of new steroidal oximes for anticancer treatment.
BIOORGANIC & MEDICINAL CHEMISTRY
(2021)
Review
Chemistry, Inorganic & Nuclear
Helene Pellissier
Summary: This review presents the recent advancements in the field of enantioselective titanium-catalyzed transformations since the beginning of 2015, demonstrating the effectiveness of chiral green titanium catalysts in promoting various types of reactions. A previous review in a book published in 2016 covered the literature up to the end of 2014. Over the past seven years, a range of highly efficient reactions have been developed.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Ilaria Caivano, Zdenek Tosner, Ivana Cisarova, David Necas, Martin Kotora
Article
Chemistry, Organic
Stefan Malatinec, Eva Bednarova, Hiroki Tanaka, Martin Kotora
Summary: This study presents a catalytic and highly enantioselective ring-opening reaction of epoxides, utilizing newly designed chiral bipyridine ligands. A Sc-complex with a newly developed bipyridine ligand demonstrated high reactivity and stereocontrol in the desymmetrization of meso-epoxides with various alcohols, achieving enantioenriched 1,2-alkoxyalcohols with high e.r. values. Additionally, attempted ring-opening of meso-epoxides with anilines showed lower enantioselectivity, dependent on the electronic effect of substituents on the aromatic ring.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Timothee Cadart, David Necas, Reinhard P. Kaiser, Ludovic Favereau, Ivana Cisarova, Robert Gyepes, Jana Hodacova, Kveta Kalikova, Lucie Bednarova, Jeanne Crassous, Martin Kotora
Summary: The enantioselective synthesis of chiral [7]-helical dispirodihydro[2,1-c]indenofluorenes (DSF-IFs) was achieved for the first time with high yields and enantioselectivity values, combining circularly polarized luminescence (CPL) activity with exceptionally high fluorescence quantum yields.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Lukas Rycek, Miguel Mateus, Nela Beytlerova, Martin Kotora
Summary: A facile and unified approach to the main selaginpulvilin's framework was achieved by catalytic [2 + 2 + 2]-cyclotrimerization of a triyne with monosubtituted alkynes using Wilkinson's catalyst. The reaction showed high ortho selectivity with reasonable yields under ambient conditions. The formal total modular syntheses of selaginpulvilin C and D were accomplished by transformation of the cyclotrimerization's products.
Article
Chemistry, Organic
Jaroslav Jacko, Monika Stasprime, Lubomir Rulisek, Ivana Cisarova, Martin Kotora
Summary: We have demonstrated that C-C bond activation in biphenylenes catalyzed by iridium, followed by reaction with tribenzocyclyne, is a suitable method for synthesizing strained and unknown monoadducts. By modifying the reaction conditions, [12]annulene products with cis and/or trans double bonds formed by hydrogen transfer can also be obtained. In addition, a [9]annulene side product was formed during the reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Ilaria Caivano, Selina Bingel, Ivana Cisarova, David Necas, Martin Kotora
Summary: The synthesis of unsymmetrical [7]-helical compounds containing the dispiro[2,1-c]indenofluorene motif has been achieved for the first time, with good yields. The key step in the reaction sequence is the catalytic intramolecular [2 + 2 + 2] cycloaddition of triynediols using various transition metal compounds (Co, Ni, etc.). The resulting cyclotrimerizations are accompanied by dehydro-Diels-Alder reactions, leading to different aromatic compounds depending on the reaction conditions. The enantioselective cyclotrimerization limits were assessed, and the structures of the products were confirmed by single-crystal X-ray diffraction analysis. Additionally, the photophysical properties of selected products were determined.
Editorial Material
Chemistry, Multidisciplinary
Hideki Yorimitsu, Martin Kotora, Nitin T. Patil
Summary: This special issue delves into the significance of transition metals in modern organic synthesis and their diverse applications in various reactions. It also highlights novel organic transformations based on transition-metal catalysis in radical chemistry and materials science fields.
Article
Chemistry, Multidisciplinary
Terezia Moravkova, Eva Bednarova, Martin Kotora
Summary: A general modular enantioselective synthetic approach was developed for the C(7)-C(18) and the C(7)-C(20) fragments belonging to E-492, actinofuranone A, and JBIR-108. The key step involves highly enantioselective crotylboration of aldehydes catalyzed by a chiral TRIP PA, leading to highly enantioenriched terminal alkenes. Followed by additional synthetic steps including Ru-catalyzed alkene cross-metathesis and Suzuki coupling reactions, the approach starts from easily available aldehydes and other reaction partners.
HELVETICA CHIMICA ACTA
(2021)
Article
Chemistry, Multidisciplinary
Jan Ulc, Yuya Asanuma, Robert Moss, Gabriele Manca, Ivana Cisarova, Martin Kotora
Summary: This study investigates the catalytic activation of C-C bonds in ring-strained compounds, followed by annulation to generate structurally more complex compounds. The location and selectivity of C-C bond activation were determined using a combination of computational predictions and experimental tests. Pentacyclic azaaromatic compounds were successfully synthesized using this approach.
Article
Chemistry, Multidisciplinary
Jesus Mendieta-Moreno, Benjamin Mallada, Bruno de la Torre, Timothee Cadart, Martin Kotora, Pavel Jelinek
Summary: In this work, the synthesis of a novel PAH molecule with an unusual C-C bond cleavage and complex molecular scaffold rearrangement is reported. It is found that the complex chemical transformation is steered by the concerted motion of individual Au-0 gold atoms on a supporting Au(111) surface. This observation highlights the importance of single-atom catalysis and catalytic activity of single Au-0 atoms in facilitating covalent carbon bond cleavage in on-surface synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Alexander A. A. Fadeev, Gabriele Manca, Martin Kotora
Summary: A synthesis of 1,4-diborylated benzenes from alkynes and ethynyl boronate was achieved using Ru-catalyzed regioselective co-cyclotrimerization. The reaction showed good applicability to alkynes with metal-coordinating groups, giving useful diborylated benzenes in modest yields. DFT calculations provided insights into the reaction mechanism and the reason for its remarkable regioselectivity. Selected diborylated benzenes were further transformed into various products, including natural bioactive small molecules like quinones and hydroquinones.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Editorial Material
Chemistry, Physical
Kotohiro Nomura, Raffaella Mancuso, Takeshi Ohkuma, Fabio Ragaini, Martin Kotora, Alfonso Grassi, Carl Redshaw, Armando Pombeiro, Ken-ichi Fujita, Carmine Capacchione, Kei Manabe, Victorio Cadierno
Article
Chemistry, Multidisciplinary
Timothee Cadart, Tim Glasel, Ivana Cisarova, Robert Gyepes, David Necas, Marko Hapke, Martin Kotora
Summary: Catalytic cyclotrimerization routes to symmetrical [9]helical indenofluorene were investigated using various transition-metal complexes and thermal conditions. The cyclotrimerizations could be accompanied by dehydro-Diels-Alder reaction, resulting in another type of aromatic compounds. The structures of both the symmetrical [9]helical cyclotrimerization product and the dehydro-Diels-Alder product were confirmed by single-crystal X-ray diffraction analyses. Enantioselective cyclotrimerization limits were also examined, and DFT calculations provided insights into the reaction course and the origin of decreased enantioselectivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Jan Ulc, Jaroslav Jacko, Ivana Cisarova, Lubomir Pospisil, David Necas, Martin Kotora
Summary: Here, the design and synthesis of a series of novel cationic nitrogen-embedded polyaromatic hydrocarbons with a planar geometry are reported. The synthesis pathway is based on catalytic C-C/C-H bond activation relay, enabling the preparation of selectively-regioselective 5,6,10,11-tetrasubstituted naphtho[2,1,8-ija]quinolizinium salts with various substituents. Single-crystal X-ray analysis confirmed the planarity of the quinolizinium core. Most of the synthesized compounds exhibited strong fluorescence, ranging from 420-600 nm, depending on the substitution pattern. DFT calculations revealed that the LUMO is always distributed over the quinolizinium framework while the delocalization of HOMO is related to the substitution pattern. Electrochemical measurements showed irreversible reduction of all compounds, which is consistent with the calculated location of LUMO orbitals.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Samuel Hruby, Jan Ulc, Ivana Cisarova, Martin Kotora
Summary: The scope of Rh-catalyzed C-C bond cleavage/annulation of biphenylene with various aromatic nitriles was investigated. Further Rh- and Ir-catalyzed C-H bond activation/annulation sequence of the resulting 9-arylphenanthridines with alkynes led to the formation of cationic [4], [5], [6] helical quinolizinium salts. The helical arrangement of these compounds was confirmed by single-crystal X-ray analysis. Most of the prepared quinolizinium salts exhibited fluorescence emission with a maximum wavelength in the range of 525-623 nm and absolute quantum yields up to 25%.
