Article
Chemistry, Multidisciplinary
Yu Wang, Rui Zhang, Jiacheng Li, Chitturi Bhujanga Rao, Xuebei Ye, Dewen Dong
Summary: A facile and efficient method for the synthesis of polysubstituted indoles has been described in this study. The method involves the use of electrophilic activation strategy with either combined Hendrickson reagent and triflic anhydride (Tf2O) or triflic acid (TfOH) to control the chemoselectivity in the intramolecular cyclodehydration. The protocol offers mild reaction conditions, simple execution, high chemoselectivity, excellent yields, and wide range of synthetic potential, making it attractive for academic research and practical applications.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Haonan Xiang, Jie Liu, Jieping Wang, Lvqi Jiang, Wenbin Yi
Summary: A method for electrophilic (fluoroalkyl) sulfenylation of nucleophiles through the collaborative use of CTAB and squaric acid to promote deoxygenation of sulfonyl derivatives is reported. Mechanistic studies show that squaric acid significantly reduces the energy barrier in the first step of deoxygenation. This novel method allows for the reduction of a wide range of functionalized sulfonyl chlorides and sulfonic anhydrides and demonstrates a high tolerance to various functional groups.
Article
Chemistry, Organic
Ying-Ying Wang, Man Liu, Lin Dong
Summary: The study successfully synthesized diverse novel compounds through Rh(iii)-catalyzed reactions, demonstrating that achieving selective activation of multiple C-H bonds in complex organic compounds is achievable.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Tian-Yi Wang, Xiao-Xuan Chen, Dong-Xing Zhu, Lung Wa Chung, Ming-Hua Xu
Summary: A highly selective C(sp(2))-H functionalization reaction catalyzed by rhodium(I)-diene has been developed, enabling the synthesis of α,β-unsaturated esters containing heteroatoms under mild reaction conditions. Mechanistic studies show that the substrate affects the reaction rate and selectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Hongbin Zhai, Miao Liu, Chao Wang, Shuxian Qiu, Jian Wei, Hongjian Yang, Yundong Wu
Summary: A novel cobalt-catalyzed reaction has been successfully developed for the annulation of benzoic hydrazides with various alkenes, leading to diverse products; the reaction is suitable for large-scale preparation and efficient removal of the directing group under mild conditions; density-functional theory calculations provide a deeper understanding of the selectivity of different alkenes.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Biology
Lenny Ferrer, Mahmoud Elsaraf, Melanie Mindt, Volker F. Wendisch
Summary: This study demonstrates that TrpB in Corynebacterium glutamicum is catalytically active even in the absence of TrpA, and can convert indole derivatives into corresponding L-tryptophan derivatives. This provides a novel approach for the production of L-tryptophan and its derivatives in biotechnology.
Article
Chemistry, Physical
Sonia Ali, Khushwinder Kaur, Jyoti Agarwal
Summary: This paper describes the synthesis of naphtho-[2,3]-furan derivatives, including naphtho-[2,3]-furan-3-yl acetate (NF), 9-nitronaphtho-[2,3]-furan-3-yl acetate (NNF), and 9-bromonaphtho-[2,3]-furan-3-yl acetate (BNF), using a multistep approach. The products were characterized by various spectroscopic techniques and their absorption and fluorescence spectra were recorded in different solvents. Solvatochromic correlations were used to estimate dipole moments. Theoretical investigations showed variation in the AEHUMO-LUMO gap. Thermogravimetric analysis confirmed the higher stability of NNF compared to BNF and NF.
JOURNAL OF MOLECULAR LIQUIDS
(2023)
Article
Chemistry, Organic
Gleiston G. Dias, Esther R. S. Paz, Juliana Y. Kadooca, Adao A. Sabino, Luiz A. Cury, Kohei Torikai, Carlos A. de Simone, Felipe Fantuzzi, Eufranio N. da Silva Junior
Summary: Rhodium(III) catalysis facilitated the C-H/N-H alkyne annulation of nonsymmetric imidazole derivatives, leading to the synthesis of rigid pi-extended imidazole derivatives with outstanding fluorescence. The study also revealed the photophysical aspects and reaction mechanism through computational calculations, providing an efficient and versatile tool for the synthesis of fluorescent compounds with a wide range of chemical and biological applications.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Elise Ane Maluf Rios, Carla M. B. Gomes, Gabriel L. Silverio, Eduardo Q. Luz, Sher Ali, Caroline da Ros Montes D'Oca, Breidi Albach, Renan B. Campos, Daniel S. Rampon
Summary: In this article, the Ag(i)-catalyzed direct selanylation of indoles with diorganoyl diselenides is described. The reaction efficiently yielded 3-selanylindoles with high regioselectivity, and it also provided direct access to 2-selanylindoles through a Plancher rearrangement-like process when the C3 position of the indole ring was blocked. Experimental analyses and density functional theory calculations were employed to elucidate the reaction mechanism. Among the considered pathways, our findings support a classic electrophilic aromatic substitution via Lewis adducts between Ag(i) and diorganoyl diselenides. The results also offer new insights into the interactions between Ag(i) and diorganoyl diselenides.
Article
Chemistry, Organic
Sundaramoorthi Sarathkumar, Veerababurao Kavala, Ching-Fa Yao
Summary: A water-soluble and low-valent rhenium(I) catalyst has been described for the C2 alkenylation of N-pyridyl/N-pyrimidyl indole derivatives with ynamides under mild conditions using water as the solvent. The reaction results in high yields of C2-Z-selective alkenylation products.
Article
Cell Biology
Cezmi A. Akdis, Mubeccel Akdis, Scott D. Boyd, Vanitha Sampath, Stephen J. Galli, Kari C. Nadeau
Summary: The prevalence of allergic diseases has been increasing worldwide in the past few decades. This review focuses on the etiology and pathophysiology of allergic diseases, exploring the roles of epithelial barriers, the immune system, climate change, and pollutants. With advancements in understanding the impact of early life, diverse diet, barriers in the skin, respiratory and gut, and the microbiome on immune tolerance to common allergens, prevention guidelines have been modified. Recent developments in the mechanisms of allergic diseases have led to effective treatments, particularly in the last 5 years, and additional treatments are currently undergoing advanced clinical trials.
SCIENCE TRANSLATIONAL MEDICINE
(2023)
Review
Pharmacology & Pharmacy
Xiaojing Li, Binbin Zhang, Yiyang Hu, Yu Zhao
Summary: Indole and its derivatives, produced by intestinal microorganisms from tryptophan metabolism, play important roles in maintaining intestinal homeostasis and impacting liver metabolism and the immune response through activation of nuclear receptors and regulation of intestinal hormones. The therapeutic prospects of indoles are promising in the treatment of intestinal and liver diseases.
FRONTIERS IN PHARMACOLOGY
(2021)
Article
Chemistry, Organic
Teng-Fei Zhao, Xiao-Li Xu, Wei-Yin Sun, Yi Lu
Summary: In this study, we report a strategy for Rh(III)-catalyzed direct ortho-C-H bond carbonylation to construct benzoxazinones from anilines and their derivatives with high atom economy. Interestingly, in situ generation of corresponding amides from anilines occurred when excess Ac2O was added and directed the following C-H bond carbonylation to form benzoxazinones. The method allows extensive functional group tolerance when alkyl amide directing groups are installed. Additionally, it shows potential application in the convenient derivatization of drugs with aryl amine groups.
Article
Chemistry, Medicinal
Pongtai Chaiputtanapun, Kriengsak Lirdprapamongkol, Bongkotrat Thanaussavadate, Thanyaporn Phongphankhum, Thanawit Thippong, Poomsith Thangsan, Phreeranat Montatip, Lukana Ngiwsara, Jisnuson Svasti, Pitak Chuawong
Summary: A series of compounds synthesized by Larock heteroannulation showed good cytotoxic activity against human lung cancer cells, through inhibition of tubulin polymerization, modulation of cell cycle, and downregulation of apoptosis-related proteins.
Article
Chemistry, Organic
Miao Li, Yaqun Dong, Cong Zhou, Junxue Bai, Jiang Cheng, Jianwei Sun, Song Sun
Summary: The iridium-catalyzed redox-neutral C-2 and C-3 dual C-H functionalization of indoles with nitrones has been developed to provide 7H-indolo[2,3-c]quinolines with high efficiency and regioselectivity. This newly developed reaction features readily available substrates, operational simplicity, broad scope, good to high efficiency, and excellent regioselectivity, which differs from previous methods.
Article
Nutrition & Dietetics
Wojciech Krezel, Aurea Rivas, Monika Szklenar, Marion Ciancia, Rosana Alvarez, Angel R. de Lera, Ralph Ruhl
Summary: The study reveals that traditional vitamin A1 is not an efficient precursor for 9CDHRA, while 9CDHROL and 9CDHBC serve as novel nutritional precursors for 9CDHRA, which are present in humans and the human food chain. Therefore, these molecules constitute a new category of vitamin, named Vitamin A5/X.
Article
Chemistry, Inorganic & Nuclear
Jonathan Alvarez-Garcia, Ramon Garcia-Lago, Jose Lorenzo Alonso-Gomez, Carlos Silva Lopez, Maria Magdalena Cid
Summary: A series of bidentate allene- and enyne-containing ligands have been synthesized and the photochemical properties of their rhenium(i) complexes have been studied. These complexes exhibit facile isomerization of the conjugated double bonds upon ambient light exposure, with efficient intersystem crossing and the consequent key role of triplet states observed in the photochemistry of these substrates upon rhenium(i) complexation.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Organic
Ioannis Stylianakis, Iraklis Litinas, Olalla Nieto Faza, Antonios Kolocouris, Carlos Silva Lopez
Summary: Indole is a common structural motif in alkaloids and has significant importance in the pharmaceutical industry. A new and elegant approach using gold(I) as a catalyst has been discovered to efficiently synthesize 7-acylindoles, and it is compatible with a wide range of reactants. The mechanism study reveals that the regioselectivity is related to the formation of an α-imino gold carbene intermediate.
JOURNAL OF PHYSICAL ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Hugo Santalla, Olalla Nieto Faza, Generosa Gomez, Yagamare Fall, Carlos Silva Lopez
Summary: A combined computational/experimental approach has revealed key mechanistic aspects of a dyotropic expansion reaction. Acid catalysis is necessary for this reaction under mild conditions. The reaction optimization has been carried out by studying different activating agents, and the reaction has shown versatility, particularly in steroid related chemistry.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Pedro Besada, Maria Gallardo-Gomez, Tania Perez-Marquez, Lucia Patino-alvarez, Sergio Pantano, Carlos Silva-Lopez, Carmen Teran, Ana Arevalo-Gomez, Aurora Ruz-Zafra, Julian Fernandez-Martin, Saida Ortolano
Summary: The study demonstrated that PBX compounds are safe and effective in stabilizing alpha-Galactosidase A in disease-relevant cellular models, as assessed by enzymatic activity measurements, molecular modelling, and cell viability assays. This experimental evidence suggests that PBX compounds are promising candidates for the treatment of Fabry disease caused by mutations that affect the folding of alpha-Galactosidase A, even for GLA variants that are not amenable to treatment with Migalastat.
Article
Chemistry, Medicinal
Immacolata Maietta, Amparo Martinez-Perez, Rosana Alvarez, Angel R. De Lera, Africa Gonzalez-Fernandez, Rosana Simon-Vazquez
Summary: Epigenetic modifications play a crucial role in the proliferation, drug resistance, and metastasis of pancreatic ductal adenocarcinoma (PDAC). In this study, researchers tested the effects of different epigenetic enzyme inhibitors and a drug that restores p53 function on PDAC cell lines. The results showed that inhibiting certain enzymes or combining drugs with gemcitabine can significantly reduce cell viability and potentially serve as a new treatment strategy for PDAC. RNA-Seq analysis also identified potential biomarkers for synergy.
Article
Plant Sciences
Aurea Rivas, Marta Castineira, Rosana Alvarez, Belen Vaz, Angel R. de Lera
Summary: The stereoselective synthesis of C40-all-trans- carotenoids with the formal hexahydrobenzofuran skeletons aurochrome, auroxanthin, and equinenone-5'8'-epoxide is reported. The synthesis is based on a one-pot or stepwise double Horner-Wadsworth-Emmons (HWE) reaction of a terminal enantiopure C15-5,6-epoxycyclohexadienylphosphonate and a central C10-trienedial. The ring expansion of the epoxycyclohexadienylphosphonate, generated by a Stille cross-coupling reaction, to the hexahydrobenzofuran skeleton was promoted by the reaction conditions of the HWE reaction prior to double-bond formation.
JOURNAL OF NATURAL PRODUCTS
(2022)
Article
Chemistry, Organic
Patricia Garcia-Dominguez, Angel R. de Lera
Summary: This study successfully synthesized several constitutional isomers of macrolactam and ruled out alternative structures of the original one through spectroscopic data comparison.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Patricia Garcia-Dominguez, Paula Lorenzo, Rosana Alvarez, Angel R. . de Lera
Summary: The total synthesis of the suggested structure of (-)-novofumigatamide was achieved, but the NMR data did not match that of the natural product. Further synthetic efforts were made to assemble alternative structures, but none of them matched the natural product. This highlights the challenges in identifying the structure of natural products.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Ikechukwu Martin Ogbu, Gulbin Kurtay, Margaux Badufle, Frederic Robert, Carlos Silva Lopez, Yannick Landais
Summary: The PIDA-mediated oxidative decarboxylation of oxamic acids in the presence of alcohols is shown to afford the corresponding urethanes under thermal conditions. Computational and experimental mechanistic exploration allows to rationalize the different reactivity of PIDA as compared to related cyclic BI-OAc and highlights the importance of the enhanced acidity of the proton in the carbamoyl radical intermediate.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Biochemistry & Molecular Biology
Claudio Martinez, Patricia Garcia-Dominguez, Rosana Alvarez, Angel R. de Lera
Summary: This article introduces the natural products containing 2,5-dioxopiperazine generated by head-to-tail cyclization of peptides, with a focus on tryptophan-derived derivatives that allow for further structural diversification. The more complex dimeric bispyrrolidinoindoline epi(poly)thiodioxopiperazines and their derivatives are also discussed. The article covers the isolation, structural characterization, biological activities, putative biogenetic routes, and synthetic efforts related to these compounds, as well as the evaluation of structurally simple analogs.
Review
Biochemistry & Molecular Biology
Torsten Bohn, Angel R. de Lera, Jean-Francois Landrier, Harald Carlsen, Daniel Merk, Tilman Todt, Jenny Renaut, Ralph Ruehl
Summary: Carotenoids are abundant lipophilic plant metabolites that have potential health benefits for humans, including reduced mortality. They can impact oxidative stress and inflammation through interactions with transcription factors. The article describes both old and new metabolic pathways of carotenoids and their bioactive derivatives, as well as the techniques and tools needed to comprehensively study this topic.
Review
Biochemistry & Molecular Biology
Patricia Garcia-Dominguez, Andrea Areal, Rosana Alvarez, Angel R. de Lera
Summary: This article covers the research progress of 2,5-dioxopiperazine-containing natural products up to the end of 2021, with a focus on those derived from tryptophan. These products exhibit diverse structures and are constructed by polyketide synthase (PKS) and nonribosomal peptide synthetase (NRPS) assembly lines. Recent studies have successfully synthesized these natural products through the mining of microbial genome sequences and competition between heterologous expression and synthetic campaigns, allowing for the investigation of their biological activities and biosynthetic pathways.
NATURAL PRODUCT REPORTS
(2022)
Article
Chemistry, Multidisciplinary
Riccardo Pedrazzani, Angela Pintus, Roberta De Ventura, Marianna Marchini, Paola Ceroni, Carlos Silva Lopez, Magda Monari, Marco Bandini
Summary: A series of modular ImPy-carbene-Au(I) complexes were synthesized and characterized in both the solid state and solution. The incorporation of oligoaryl units at the C5-position of the ImPy core resulted in fine-tunable and predictable catalytic properties of the organometallic species. The presence of a CF3-containing aromatic ring at the ImPy core significantly accelerated several [Au(I)]-catalyzed electrophilic activations of unsaturated hydrocarbons.
ACS ORGANIC & INORGANIC AU
(2022)
Article
Chemistry, Multidisciplinary
Lucia Guillade, Paula Mora, Pedro Villar, Rosana Alvarez, Angel R. de Lera
Summary: This study achieved the total synthesis of the natural product nahuoic acid A by synthesizing a non-conjugated pentaenal precursor with high stereoselectivity, demonstrating the formation of different products under different reaction conditions.
