Article
Chemistry, Organic
Davit Hayrapetyan, Valeriya Stepanova
Summary: In this study, spirocyclic pyrrolidones and piperidones were synthesized via [3+2]- and [3+3]-aza-annulation reactions starting from readily available alpha-ketolactones and alpha-ketolactams. The annulation reactions proceeded with good yields and excellent diastereoselectivity, creating one C-C and two C-N bonds, as well as three new stereocenters in a fast and efficient manner.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Biochemistry & Molecular Biology
Olga Bakulina, Anna Inyutina, Dmitry Dar'in, Mikhail Krasavin
Summary: This review summarizes recent developments in multicomponent reactions of diazo compounds, analyzing the role of diazo reagents and the type of interaction between components. In contrast to previous reviews mostly focused on metal catalyzed transformations, this work covers a substantial amount of organocatalytic or catalyst-free methodologies.
Article
Chemistry, Multidisciplinary
Justus Reitz, Patrick W. Antoni, Julian J. Holstein, Max M. Hansmann
Summary: Recently, stable diazoalkenes have gained attention in organic chemistry as a new substance class. A general synthetic approach using a Regitz-type diazo transfer with azides is established, which allows for the synthesis of pyridine diazoalkenes. This approach is applicable to weakly polarized olefins as well. The properties of these pyridine-derived diazoalkenes are distinct from previously reported classes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Yan Long, Yun Wang, Yue-You Chen, Wen-Yong Han, Nan-Wei Wan, Wei-Cheng Yuan, Yong-Zheng Chen, Bao-Dong Cui
Summary: This article describes an inexpensive copper-catalyzed sequential reaction process for synthesizing structurally diverse spiro-dihydropmolo[1,2-a]quinoxaline derivatives. The significance of this method is highlighted by its ability to convert synthetic compounds into potentially bioactive molecules.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Yong-Liang Su, Geng-Xin Liu, Luca De Angelis, Ru He, Ammar Al-Sayyed, Kirk S. Schanze, Wen-Hao Hu, Huang Qiu, Michael P. Doyle
Summary: This study demonstrates the efficient generation of functionalized derivatives through photocatalyzed multicomponent reactions using nitrogen aromatic heterocycles, alkenes, and diazo compounds. The reaction shows high functional group tolerance and exacting regioselectivities. Mechanistic studies, including photophysical measurements, provide insights into this radical cascade reaction.
Article
Biochemistry & Molecular Biology
Yulia A. Antonova, Yulia V. Nelyubina, Sema L. Ioffe, Andrey A. Tabolin
Summary: A Rh(II)-catalyzed reaction of cyclic nitronates with vinyl diazoacetates proceeds as an annulation reaction, producing bicyclic unsaturated nitroso acetals. Optimization of reaction conditions revealed the use of Rh(II) octanoate as the preferred catalyst in THF at room temperature, allowing the preparation of target products in good yields and excellent diastereoselectivity. Under basic conditions, these nitroso acetals undergo ring contraction into the corresponding pyrroles, and both transformations can be performed in a one-pot fashion.
Article
Chemistry, Organic
Junrong Chen, Muhammad Suleman, Ping Lu, Yanguang Wang
Summary: A Rh(III)-catalyzed [4+1] annulation of aromatic carboxylic acids with 4-diazoisoquinolin-3-ones was reported. A library of highly substituted spiro [isobenzofuran-1,4'-isoquinoline]-3,3'-diones were synthesized in moderate to good yields by this protocol (30 examples, up to 84% yield). The merits of this protocol are broad substrate scope, readily available starting materials, mild reaction conditions, and scalability.
Review
Chemistry, Organic
Pooja Soam, Priya Kamboj, Vikas Tyagi
Summary: This review discusses the use of diazo compounds as carbene precursors in synthetic chemistry, particularly focusing on the generation of metal bound carbenes with the help of metal catalysts, with rhodium being a widely used catalyst for cascade reactions involving carbene transfer. The efforts made in the past five years towards the synthesis of important heterocyclic compounds through rhodium-catalyzed cascade reactions are also covered in this review.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Jingya Yang, Wentong Ma, Shengyu Wang, Jiangjiang Li, Hongyan Zhou
Summary: A visible-light-mediated cycloaddition method for the synthesis of 1,2,4-triazolidines has been developed. Using the organic dye rose bengal as a photocatalyst and alkyl tertiary amines as precursors, the reaction proceeded smoothly under visible light irradiation at room temperature, yielding the desired products with high yields.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Ouldouz Ghashghaei, Marina Pedrola, Francesca Seghetti, Victor V. Martin, Ricardo Zavarce, Michal Babiak, Jiri Novacek, Frederick Hartung, Katharina M. Rolfes, Thomas Haarmann-Stemmann, Rodolfo Lavilla
Summary: The participation of reactants in polarity inversion allows the continuation of productive domino processes in multicomponent reactions, leading to the discovery of novel reaction pathways and various polyheterocyclic scaffolds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Laieli S. Munaretto, Caio Y. dos Santos, Rafael D. C. Gallo, Celso Y. Okada Jr, Victor M. Deflon, Igor D. Jurberg
Summary: Two new visible-light-mediated strategies are described using aryldiazoacetates, resulting in the generation of imines and furan-3(2H)-ones. These strategies involve the photolysis of aryldiazoacetates and the photochemically promoted Wolff rearrangement of aryldiazoketones.
Article
Chemistry, Applied
Yasuaki Fukazawa, Vladimir Yu. Vaganov, Julia V. Burykina, Artem N. Fakhrutdinov, Ruslan I. Safiullin, Felix Plasser, Aleksandr E. Rubtsov, Valentine P. Ananikov, Andrei V. Malkov
Summary: The mechanism of metal-catalyzed asymmetric alkylation of indoles remains uncertain. In this study, the authors investigate the mechanism from both molecular and nano-level perspectives, revealing the role of water and catalyst precursor on reaction selectivity and performance.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Josipa Suc Sajko, Ivanka Jeric
Summary: A structurally diverse library of chiral N beta-substituted 1,2-diazetidin-3-ones was synthesized using a 4-center 3-component Ugi reaction, with unprotected alpha-hydrazino acids. Various isocyanides and carbonyl compounds, including both aldehydes and ketones, were used. Furthermore, postcondensation modifications at three different sites were demonstrated.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Minghui Qi, Muhammad Suleman, Jiale Fan, Ping Lu, Yanguang Wang
Summary: Here, a copper(I)-catalyzed ring expansion reaction of isoxazoles with 4-diazoisoquinolin-3ones is reported, providing a series of densely substituted novel spiro[isoquinoline-4,2'-[1,3]oxazin]-3-ones in good to excellent yields. The prominent features of this methodology include broad substrate scope, readily available starting materials, cheap catalyst, mild reaction conditions, and scalability.
Article
Chemistry, Physical
Zi-Sheng Chen, Xiao-Yan Huang, Qing Liu, De-Xin Song, Fang Yang, Kegong Ji
Summary: This article presents a synergistic Rh(II)/Pd(0) dual-catalyzed strategy for the three-component oxy-allylation of a-diazo esters, alcohols, and allylic benzoates. The reaction involves the trapping of active protic oxonium ylides with catalytic p-allyl Pd(II) intermediates. Interestingly, water also participates in the reaction through a different allylic migratory insertion of palladium-carbenes. These transformations offer a straightforward approach to various a-ternary allylated carboxylic esters using readily available starting materials under redox-neutral conditions, leading to the successive generation of two new C-O and C-C bonds at the carbene center. CO 2022 Elsevier Inc. All rights reserved.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Applied
Irene Martin, Cristina Aragoncillo, Pedro Almendros
Summary: This research has achieved a selective palladium-catalyzed reaction sequence, leading to the synthesis of novel 2-iodo-1-aryl-9H-carbazoles. The observed formation of 2-iodocarbazoles in contrast to gold catalysis suggests a metal-controlled cyclization through chemo- and regioselective alkyl migration and iodonium migration.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Review
Chemistry, Multidisciplinary
Jose M. Alonso, Pedro Almendros
Summary: The allene functionality, specifically the allenol, has evolved from a chemical curiosity to a common building block in modern organic chemistry, with unique reactivity and frequent occurrence in naturally systems. This Review highlights the significant contributions to the chemistry of allenols in the past decade, focusing on their synthesis, reactivity, and presence in natural products.
Article
Chemistry, Organic
Carlos Lazaro-Milla, Hikaru Yanai, Pedro Almendros
Summary: A new sequential cyclization cascade method has been successfully developed in this study for the efficient preparation of functionalized tricyclic indoline cores bearing two contiguous stereocenters.
Article
Chemistry, Applied
Fernando Herrera, Pablo Esteban, Amparo Luna, Pedro Almendros
Summary: The synergy between metal catalysis and radical chemistry has enabled researchers to overcome previous limitations in reactions between allenols and sulfonylating reagents, leading to successful copper-catalyzed cascade cycloetherification/sulfonylation for the controlled preparation of specific products.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Shoki Hoshikawa, Hikaru Yanai, Irene Martin-Mejias, Carlos Lazaro-Milla, Cristina Aragoncillo, Pedro Almendros, Takashi Matsumoto
Summary: The carboarylation reaction of biphenyl-alkynes was successfully initiated by electrophilic attack of 1,1-bis(triflyl)ethylene on the alkyne moiety, resulting in polycyclic aromatic hydrocarbons decorated with superacidic carbon acid functionality. Neutralization of the obtained acids with NaHCO3 produced sodium salts with improved solubility in both aqueous and organic solvents.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Carlos Lazaro-Milla, Pedro Almendros
Summary: This study presents a sustainable and efficient synthesis of new quinoline derivatives with one or two SO2CF3 groups, without the need for metal, catalyst, or irradiation. The method uses readily available and stable precursors, avoiding the formation of side products, while being able to tolerate a wide range of functional groups under mild conditions.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Applied
Irene Martin-Mejias, A. Sonia Petcu, Jose M. Alonso, Cristina Aragoncillo, Pedro Almendros
Summary: The controlled access to 1-aryl 2,3-diiodo-carbazoles involving iodine transposition has been achieved directly from acyclic precursors. The 2,3-diiodo-carbazole core is susceptible to further chemoselective decoration at C3-I or double difunctionalization.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Physical
Mireia Toledano-Pinedo, Teresa Martinez del Campo, Hikaru Yanai, Pedro Almendros
Summary: This study presents a gold-catalyzed bis[(trifluoromethyl)sulfonyl]ethylation of alpha-allenols, allowing the synthesis of sterically congested bis(triflyl)enals with quaternary carbon centers. The reaction pathway is different from the conventional approach, as Au(I) acts as a pi-Lewis base catalyst instead of a pi-Lewis acid, activating the allene and facilitating the unusual addition of a carbon nucleophile from the gold complex belonging to the allenol moiety. Density functional theory calculations were performed to understand this unique pathway.
Review
Chemistry, Applied
Jose M. Alonso, Pedro Almendros
Summary: Conjugated and non-conjugated allenones are widely used in organic synthesis, natural products, and mechanistic investigations due to their unique properties and applications. Their ability to form cycles allows for the preparation of strained systems, medium-sized rings, arenes, heterocycles, and complex polycycles. This comprehensive review provides an overview of the synthetic possibilities offered by allenones, inspiring the organic chemistry community in their search for more efficient synthetic methodologies, preparation of biological and pharmaceutical targets, and advancing theoretical organic chemistry knowledge. The review also discusses synthetic aspects, catalysis innovation, and mechanistic insights related to the allenone motif, as well as examples of total synthesis and pharmacologically active compounds. It aims to attract researchers from various fields including organic chemistry, synthetic chemistry, catalysis, theoretical chemistry, natural products, and medicinal chemistry.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
A. Sonia Petcu, Carlos Lazaro-Milla, F. Javier Rodriguez, Isabel Iriepa, Oscar M. Bautista-Aguilera, Cristina Aragoncillo, Jose M. Alonso, Pedro Almendros
Summary: Here, a convenient preparation method for isocoumarin and isoquinolone is described, which involves an initial bis(triflyl)ethylation reaction followed by heterocyclization. The efficiency of the reaction depends on the substituents' electronic nature in the precursors. Molecular docking of the obtained isocoumarins showed promising biological activities on human acetylcholinesterase.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Diego G. Matesanz, Laura Gamarra, Teresa Martinez del Campo, Pedro Almendros, Sara Cembellin
Summary: A highly selective Mn(I)-catalyzed dienylation of arenes and heteroarenes with acetylated allenes is reported. The method proceeds through a one-pot procedure and delivers linear 1,3-dienes as single products with high stereoselectivity and total regioselectivity. This strategy shows wide functional group tolerance and preparative scale utility, making it efficient for late-stage functionalization of complex valuable molecules. The synthetic importance is highlighted by different derivatizations of the final products, which can exhibit interesting fluorescence properties.
Article
Chemistry, Organic
Hikaru Yanai, M. Rosa Marquez, Sara Cembellin, Teresa Martinez del Campo, Pedro Almendros
Summary: An indium-promoted lactonization of (indol-3-yl)-2-oxoacetaldehydes, allowing the synthesis of substituted gamma-methylenebutenolides in water, has been achieved. This process differs from the established reactivity of unsaturated organic halides and carbonyls mediated by metals. The use of water as a medium and the ease of purification make this protocol a convenient and sustainable synthetic strategy. A plausible reaction pathway has been proposed with the aid of density functional theory calculations.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Physical
Mireia Toledano-Pinedo, Teresa Martinez del Campo, Hikaru Yanai, Pedro Almendros
Summary: The gold-catalyzed bis[(trifluoromethyl)sulfonyl]ethylation of alpha-allenols, allowing the synthesis of sterically congested bis(triflyl)enals with quaternary carbon centers, is presented. In this reaction, a unique pathway is observed where Au(I) acts as a pi-Lewis base catalyst instead of a pi-Lewis acid to activate the allene, enabling the unusual addition of a carbon nucleophile. Density functional theory calculations were conducted to analyze this unconventional pathway.
Article
Chemistry, Multidisciplinary
Carlos Lazaro-Milla, M. Teresa Quiros, Diego J. Cardenas, Pedro Almendros
Summary: The synthesis of skipped 1,4-enynes through functionalization of the cyclobutene core with alkynes has been achieved, indicating an unusual pathway of oxidative addition in tertiary iodoalkanes.
CHEMICAL COMMUNICATIONS
(2021)
