Article
Chemistry, Organic
Anding Li, Ziru He, Bingyan Liu, Zhen Yang, Zichun Zhang
Summary: In this study, a concise and stereoselective total synthesis of (+/-)-cephanolide B was accomplished in 15 steps. The key steps in the synthesis included an intermolecular Diels-Alder reaction, a tandem reaction featuring intramolecular Pauson-Khand reaction, 6 pi-electrocyclization, and oxidative aromatization to construct the ABC-tricyclic rings (6-5-6), as well as a phthaloyl peroxide-mediated arene oxygenation to install the C-13 phenol group.
Review
Chemistry, Multidisciplinary
Zhen Yang
Summary: The total synthesis endeavors contribute to the discovery and invention of new synthetic reactions to advance organic synthesis. Bioactive compounds share common features, such as molecular complexity, protein-binding ability, structural rigidity, and three-dimensionality. Total synthesis offers an alternative solution for generating scarce natural products and their derivatives for studying their biological functions.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Multidisciplinary
Lisa-Catherine Rosenbaum, Maximilian Haefner, Tanja Gaich
Summary: A racemic and scalable enantioselective total synthesis of (+)-waihoensene was achieved, featuring an angular triquinane substructure with an all-cis-fused tetracyclic backbone and six contiguous stereocenters, four of which are quaternary. Enantioselectivity was introduced at an early stage, and key structural features were efficiently installed through several diastereoselective reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Hui Wang, Yi Liu, Hongyuan Zhang, Baochao Yang, Haibing He, Shuanhu Gao
Summary: The asymmetric total syntheses of cephalotaxus C19 diterpenoids, which possess a unique cycloheptene A ring with a chiralmethyl group at C-12, were achieved using a universal strategy. Six members, including previously unreported compounds, were successfully synthesized. The concise approach involved a Nicholas/Hosomi-Sakurai cascade reaction to generate the cycloheptene ring with a chiral methyl group, followed by an intramolecular Pauson-Khand reaction for the construction of the target molecules' complete skeleton. This work provides a new strategy for the synthetic analysis of cephalotaxus diterpenoids and structurally related natural products.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Paul Shaw, Storm J. Hassell-Hart, Gayle E. Douglas, Andrew G. Malcolm, Alan R. Kennedy, Gemma White, Laura C. Paterson, William J. Kerr
Summary: In this study, we applied silyl enol ether moieties as efficient alkene coupling partners within cobalt-mediated intramolecular Pauson-Khand reactions. This cyclization strategy delivers valuable oxygenated cyclopentenone products in high yields and allows for the incorporation of a variety of decorated structures.
Article
Chemistry, Multidisciplinary
Ridge Michael P. Ylagan, Eric Jaewon Lee, Daniela E. Negru, Paolo Ricci, Bohyun Park, Haram Ryu, Mu-Hyun Baik, P. Andrew Evans
Summary: We report an enantioselective rhodium(I)-catalyzed Pauson-Khand reaction using 1,6-chloroenynes that contain challenging 1,1-disubstituted olefins. Unlike previous studies, this new approach allows for a wider range of substrates, including both carbon and heteroatom tethers with polar and non-polar substituents on the alkene. DFT calculations reveal the critical role of the halide, which pre-polarizes the alkyne and provides the appropriate steric profile for a favorable interaction with the chiral diphosphine ligand.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Jisna Jose, Thomas Mathew
Summary: 2-Cyclopentenone and its derivatives are highly esteemed synthetic intermediates with exceptional utility in organic synthesis. They are favored structural motifs in numerous pharmaceutical drugs and natural products, highlighting their significance. The review discusses the various methods used to synthesize cyclopentenones from 2016 to 2023.
Article
Chemistry, Organic
Jorge Escorihuela
Summary: In this study, density functional theory calculations are used to clarify the mechanism and reactivity of enynes containing a vinyl fluoride moiety for the Co2(CO)(8)-mediated intramolecular Pauson-Khand reaction. The results show that alkene insertion is the rate-determining step for this reaction. The effect of substituents on the reaction has also been investigated, with fluorinated enynes having lower reactivity compared to malonate homologues.
SYNTHESIS-STUTTGART
(2023)
Review
Chemistry, Organic
Sambasivarao Kotha, Ambareen Fatma
Summary: This article highlights various synthetic methodologies related to tetraquinane frameworks in crinipellin derivatives, including different synthetic strategies and emphasis on the core structure research.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Alison R. Cochrane, William J. Kerr, Laura C. Paterson, Colin M. Pearson, Paul Shaw
Summary: The development of a sulfide-promoted, microwave-assisted Pauson-Khand reaction enables the formation of fused cyclopentenones using sub-stoichiometric quantities of a cobalt mediator in rapid reaction times and without the need for an external source of toxic carbon monoxide gas. This protocol is applicable to both intra- and intermolecular Pauson-Khand reaction examples.
Article
Chemistry, Organic
Chong-Chong Chen, Zhiqiang Ren, Zhongliu Sun, Zezhong Sun, Xin Shu, Yunxia Wang, Xiangdong Hu
Summary: Cephalotaxus diterpenoids are attractive natural products with diverse chemical structures and valuable biological activities. This study developed a diastereoselective Pauson-Khand reaction as an effective strategy for synthesizing the core structure of these compounds, leading to the total synthesis of several compounds.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Annah E. Kalb, Mingxin Liu, Megan Bosso, Christopher Uyeda
Summary: A dinickel catalyst is used to promote the [2 + 2 + 1]-cycloaddition reaction of two aldehyde equivalents and a vinylidene, leading to the synthesis of unsymmetrical alkyl-substituted α-hydroxy ketones. Mechanistic studies show that migratory insertion of the aldehyde and C-O reductive elimination are crucial steps, and under dilute conditions, an enone side product is formed due to competing β-hydride elimination.
Article
Chemistry, Multidisciplinary
Tianhao Ma, Hao Cheng, Mallesham Pitchakuntla, Weihao Ma, Yanxing Jia
Summary: We have achieved the first total synthesis of (-)-principinol C, which is a natural product with an intriguing and complex 5/7/6/5 tetracyclic skeleton and eight contiguous stereocenters. The key step in assembling the 5/7/6/5 tetracyclic skeleton was the intramolecular Pauson-Khand reaction. This synthetic route represents the first application of intramolecular Pauson-Khand reaction of enyne to construct the 7,5-bicyclic ring system in natural product synthesis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Applied
Ding Ma, Naifeng Hu, Junli Ao, Shaoli Zang, Guo Yu, Guangxin Liang
Summary: Pauson-Khand reactions with concomitant C-O bond cleavage have been developed for constructing complex bicyclic ring systems with precise control over regio- and stereochemistry. The mechanism behind this reaction has been proposed based on deuterium labelling experiments.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Maria Biosca, Daniel Tarr, Oscar Pamies, Montserrat Dieguez
Summary: Pd-catalyzed asymmetric allylic substitution (AAS) is an effective method for producing chiral molecules with alkene-substituted frameworks. Phosphite-oxazolines have emerged as strong candidates to be privileged ligands, providing high enantiocontrol in the Pd-AAS of various substrates and nucleophiles. This review discusses the progress made in the design of tailor-made phosphite-oxazoline ligand libraries for the Pd-AAS and its application in the construction of chiral complex molecules.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Albert Cabre, Xavier Verdaguer, Antoni Riera
Summary: This review provides an overview of the recent advances in the asymmetric hydrogenation (AH) synthesis of chiral amines reported from 2010 to 2020. Various types of chiral amines, including imines, enamides, enamines, allyl amines, and N-heteroaromatic compounds, are discussed.
Article
Chemistry, Multidisciplinary
Pep Rojo, Medea Molinari, Albert Cabre, Clara Garcia-Mateos, Antoni Riera, Xavier Verdaguer
Summary: Chiral compounds containing nitrogen heteroatoms are crucial for the chemical, pharmaceutical, and agrochemical industries. In this study, a series of P-stereogenic phosphinooxazoline iridium catalysts were synthesized and successfully used in the asymmetric hydrogenation of N-Boc-2,3-diarylallyl amines, achieving high enantioselectivity. The synthetic utility of the obtained 2,3-diarylpropyl amines was also demonstrated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Medicinal
Guillem Loren, Irene Espuny, Alicia Llorente, Craig Donoghue, Xavier Verdaguer, Roger R. Gomis, Antoni Riera
Summary: In the treatment of breast cancer, targeting the estrogen receptor signaling pathway has been a major strategy. However, resistance to hormone blockade is a common issue. This study designed and synthesized a series of proteolysis targeting chimeras (PROTACs) that can induce the degradation of estrogen receptor alpha in breast cancer cells. TVHL-1, a potent ERα degrader, was discovered and could serve as a valuable tool for biological study and potential therapeutics.
EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY
(2022)
Article
Chemistry, Organic
Ruben Alvarez-Yebra, Ricard Lopez-Coll, Pere Galan-Masferrer, Agusti Lledo
Summary: We have reported a chiral deep cavitand receptor based on calix[5]arene, which is stabilized by a cooperative network of hydrogen bonds and has a highly flexible structure. The cavitand exhibits enantioselective molecular recognition with a series of chiral quaternary ammonium salts, leading to unprecedented stability ratios between the corresponding diastereomeric host-guest complexes. Molecular dynamics simulations confirm the higher flexibility of the new host and the emergence of superior induced-fit behavior compared to resorcin[4]arene derived self-folding cavitands.
Article
Chemistry, Organic
Marina Bellido, Carlos Riego-Mejias, Alejandro Diaz-Moreno, Xavier Verdaguer, Antoni Riera
Summary: A novel method for preparing chiral methyl benzylic compounds is described, involving the preparation of terminal homoallyl sulfones from homoallyl alcohols through Lewis acid isomerization of oxetanes. Asymmetric hydrogenation of these homoallylic sulfones using an iridium catalyst yielded gamma-chiral sulfones with high enantioselectivities (up to 98% ee). The synthetic potential of this method was demonstrated through the total synthesis of (R)-(-)-curcumene.
Article
Chemistry, Physical
Maria Biosca, Pol de la Cruz-Sanchez, Jorge Faiges, Jessica Margalef, Ernest Salomo, Antoni Riera, Xavier Verdaguer, Joan Ferre, Feliu Maseras, Maria Besora, Oscar Pamies, Montserrat Dieguez
Summary: Ir-MaxPHOX-type catalysts exhibit high catalytic performance in the hydrogenation of a wide range of nonchelating olefins with different geometries, substitution patterns, and degrees of functionalization. These air-stable and readily available catalysts have been successfully used in the asymmetric hydrogenation of di-, tri-, and tetrasubstituted olefins (ee ' s up to 9996). The combination of theoretical calculations and deuterium labeling experiments has revealed the factors responsible for the observed enantioselectivity, allowing for the rationalization of suitable substrates for these Ircatalysts.
Review
Chemistry, Inorganic & Nuclear
Pep Rojo, Antoni Riera, Xavier Verdaguer
Summary: Since the development of BisP* ligand by Imamoto, P-stereogenic phosphines bearing a bulky tert-butyl group and a smaller alkyl group have shown remarkable performance in various asymmetric processes. Advances in this class of ligands include the introduction of more rigid backbones, the three-hindered quadrant concept, and the substitution of tert-butyl group with adamantyl. The industrial sector has also contributed by reporting successful P-stereogenic Buchwald-type monophosphines for asymmetric coupling reactions. This review focuses on the synthesis and applications of bulky P-stereogenic phosphines developed since the late 1990s, with a special emphasis on ligands successfully applied in asymmetric catalysis.
COORDINATION CHEMISTRY REVIEWS
(2023)
Review
Chemistry, Multidisciplinary
Ruben Alvarez-Yebra, Ricard Lopez-Coll, Nuria Clos-Garrido, David Lozano, Agusti Lledo
Summary: Self-folding cavitands are bioinspired synthetic receptors that mimic the host-guest chemistry of biomolecules. The development of confined spaces that replicate the flexible nature of biological receptors is an unaddressed issue. This review summarizes the development of a new family of calix[5]arene derived self-folding cavitands that exhibit enhanced induced fit and conformational selection phenomena, using hydrogen bonding preorganization.
ISRAEL JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Ruben Alvarez-Yebra, Alba Sors-Vendrell, Agusti Lledo
Summary: We present a readily available cavitand receptor based on calix[5]arene, which is stabilized in the closed cone conformer through intermolecular hydrogen bonding with methanol molecules. The receptor has a highly spherical aromatic surface that binds C60 and C70 fullerenes effectively, and the binding event can be regulated by the addition of methanol.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Enric Ros, Marina Bellido, Joan A. Matarin, Albert Gallen, Manuel Martinez, Laura Rodriguez, Xavier Verdaguer, Lluis Ribas de Pouplana, Antoni Riera
Summary: A set of 3-bromo-1,2,4,5-tetrazines with distinct substitutions have been used as reagents for late-stage functionalization. Spectroscopic studies showed that tetrazine ethers are intrinsically fluorescent and this fluorescence can be lost through iEDDA cycloaddition. Tetrazine-phenol ethers can undergo rapid iEDDA reactions with a second order rate constant compatible with bioorthogonal ligations. The coupling of 3-bromo-6-methyl-1,2,4,5-tetrazine with l-tyrosine and octreotide demonstrated the detection and reactivity of intrinsically fluorescent tetrazines in a biologically relevant context. The synthesis and characterization of fluorescent tetrazine ethers with bioorthogonal applicability pave the way for the generation of useful compounds for both detection and bioconjugation in vivo.
Review
Chemistry, Multidisciplinary
Dan He, Yawen Li, Fuwen Zhao, Yuze Lin
Summary: High trap density in organic solar cells leads to localized charge carriers and reduced carrier lifetime, limiting device efficiency. This feature article summarizes the recent advances of trap suppression by material design and device engineering.
CHEMICAL COMMUNICATIONS
(2024)
Review
Chemistry, Multidisciplinary
Olivier Monfort, Arshitha Madhusudhan, Martin Motola
Summary: This article presents the advantages of coupling photocatalysis and Fenton-based processes for environmental remediation and discusses their synergy. It critically examines the simultaneous triggering of these two processes and provides insights into research approaches. The study aims to enhance understanding of this complex process and highlight the potential integration of new catalysts in current wastewater treatment technology.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Manideepa Dhar, Chittaranjan Mishra, Avijit Das, Uttam Manna
Summary: An approach of 'polymerization of monomers in its aggregated form' has been introduced to tailor the water wettability of fibrous and porous substrates, achieving hydrophobicity to superhydrophobicity transition, as well as patterned wettability. This facile chemical method provides a durable coating with adjustable and patterned wettability for various potential applications.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Saswat Ranjan Bhoi, Chhanda Debnath, Shikha Gandhi
Summary: In this article, a novel catalytic reaction using Pd(0) and Bronsted acid is reported for the synthesis of biologically important imidazolidinone-fused N-heterocycles through redox-neutral intramolecular N-allylation of indoles and pyrroles with alkynes. This atom-economical method is applicable to a wide range of substrates and eliminates the need for leaving groups or oxidizing agents commonly used in traditional allylation reactions.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Longkun Chen, Mingshuai Zhang, Meichen Liu, Zhuoyuan Liu, Yuetong Qiu, Zhilai Zhang, Fuchao Yu, Jiuzhong Huang
Summary: In this study, an efficient Rh(III)-catalyzed selective mono- and dual-C-H bond functionalization/cyclization with iodonium ylide as the sole coupling partner was demonstrated. Fused benzodiazepine skeletons were obtained in excellent yields, providing an improved approach to dual C-H unsymmetrical functionalization.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Alice Kennett, Sven Epple, Gabriella van der Valk, Irene Georgiou, Evelyne Gout, Romain R. Vives, Angela J. Russell
Summary: This study presents the design and synthesis of sulfated disaccharide inhibitors based on IdoA(2S)-GlcNS(6S), which showed potent inhibition of Sulf-2. The results suggest that IdoA(2S)-GlcNS(6S) is the shortest fragment size required for effective inhibition of Sulfs, and a trisulfated disaccharide is identified as the minimal fragment size of heparan sulfate for effective endosulfatase inhibition.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Mauro Garbini, Andrea Brunetti, Riccardo Pedrazzani, Magda Monari, Massimo Marcaccio, Giulio Bertuzzi, Marco Bandini
Summary: The self-adaptability of galvanostatic electrolysis was found to be helpful in a multistage chemo- and diastereoselective electrochemically promoted cyclodimerization of chalcones. Through a series of reductive events, densely functionalized cyclopentanes with five contiguous stereocenters were obtained (25 examples, yields up to 95%, dr values up to >20:1). Further experimental and electrochemical investigations indicated the crucial role of dynamic kinetic resolution of the aldol intermediate in the reaction mechanism.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Dhananjay S. Nipate, Neha Meena, Prakash N. Swami, Krishnan Rangan, Anil Kumar
Summary: In this study, the synthesis of functionalized benzo[a]phenazines and indazolo[2,3-a]quinolines was achieved through Rh(III)-catalyzed oxidative annulation of 2-arylquinoxalines and 2-aryl-2H-indazoles with allyl alcohols. The method showed a wide substrate scope, excellent functional group tolerance, good to high yields of annulated products, and the capability for scaled-up synthesis. A tentative mechanism of the annulation reaction was proposed based on a preliminary mechanistic investigation.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Ruonan Zhang, Abudukadi Tudi, Xia Yang, Xuping Wang, Zhihua Yang, Shujuan Han, Shilie Pan
Summary: A new lead tellurium borate material with a unique fundamental building block [B4O10] was synthesized and found to exhibit high birefringence. The structure-property relationship was discussed using first-principles calculations.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Amresh Kumar Singh, Baishali Thakurta, Anupam Giri, Monalisa Pal
Summary: This study introduces three key concepts for the quick synthesis of large-scale high-quality 2D materials films and their utilization in device fabrication.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Reina Hagiwara, Shun Nishimura, Kosuke Okeyoshi
Summary: A copolymer-conjugated nanocatalytic system has been developed to improve electron transfer and enhance photoinduced H2 generation.
CHEMICAL COMMUNICATIONS
(2024)
