Article
Chemistry, Multidisciplinary
Marta Solas, Miguel A. Munoz-Torres, Fernando Martinez-Lara, Lorena Renedo, Samuel Suarez-Pantiga, Roberto Sanz
Summary: A wide variety of regioselectively substituted carbazole derivatives can be synthesized by controlling the oxidation state of the gold catalyst and the electronic nature of the substituents of the alkynol moiety. The regioselectivity of the reaction can be controlled to achieve different substitution patterns.
Article
Chemistry, Organic
Qiuling Song, Fumei Ke, Changjiang Yu, Xin Li, Heyun Sheng
Summary: A convenient method for synthesizing fluorine-containing heterocyclic compounds was developed, involving copper-catalyzed free radical addition and molecular lactone exchange of alkynol and ethyl bromodifluoroacetate. This method offers easy availability of raw materials, good stereochemical selectivity, and simple operation. It also allows for the synthesis of valuable tetrasubstituted E-configurated alkenes and various vinyl C-Br bonds and difluoromethylene-containing functionalized heterocycles.
Article
Chemistry, Organic
Jian Li, Yang Liu, Zebin Chen, Jiaming Li, Xiaoliang Ji, Lu Chen, Yubing Huang, Qiang Liu, Yibiao Li
Summary: A method for obtaining substituted thiophenes with functional potential through metal-free dehydration and sulfur cyclization was described. The reaction of alkynols with elemental sulfur (S-8) or EtOCS2K yielded moderate-to-good yields. The method showcased the base-free generation of a trisulfur radical anion (S-3(center dot-)) and its addition to alkynes as an initiator. This research broadens the applications of S-3(center dot-) in the synthesis of sulfur-containing heterocycles.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Cunbo Wei, Jiawen Wu, Lizhu Zhang, Zhonghua Xia
Summary: A highly selective synthesis of Z-alkenyl indoles was developed by adding indoles to haloalkynes using a gold catalyst and a cocatalyst, resulting in high yields at room temperature.
Article
Chemistry, Multidisciplinary
Sagar R. Mudshinge, Yuhao Yang, Bo Xu, Gerald B. Hammond, Zhichao Lu
Summary: The first C-SCF3/SeCF3 cross-coupling reactions using gold redox catalysis are reported. The new method enables the one-stop synthesis of aryl/alkenyl/alkynyl trifluoromethylthio- and selenoethers, with a broad substrate scope. It is scalable and can be applied to late-stage functionalization of bioactive molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Shiwei Li, Huachao Zhao, Wei Ran, Jingfu Liu, Rui Liu
Summary: Au@RhPd ultrathin nanowires serve as a highly reactive and selective catalyst for the hydrogenation of phenol at ambient conditions. The interaction between Au NWs and Rh atoms enhances the adsorption and desorption processes, while Pd acts as a cocatalyst to activate H2 and transfer it to Rh sites. This catalyst exhibits a turnover frequency of up to 560 h(-1) with over 80% selectivity towards cyclohexanones.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Yao Ge, Fei Ye, Ji Yang, Anke Spannenberg, Ralf Jackstell, Matthias Beller
Summary: A novel palladium-catalyzed aminocarbonylation of alkynols for the synthesis of substituted itaconimdes has been reported, showcasing high catalyst activity and excellent selectivity. The method allows for the synthesis of various interesting heterocycles through the use of a unique catalyst system and appropriate reaction conditions. Mechanistic studies highlight the crucial role of the hydroxyl group in the substrate for controlling selectivity.
Article
Chemistry, Multidisciplinary
Qing-Yun Fang, Jie Han, Mingzhe Qin, Weipeng Li, Chengjian Zhu, Jin Xie
Summary: Reported here is a three-component 1,2-difunctionalization reaction of alkenes, unactivated alkyl bromides, and nucleophiles (e.g., amines and indoles) using a trinuclear gold catalyst [Au-3(tppm)(2)](OTf)(3). This reaction enables facile 1,2-aminoalkylation and 1,2-alkylarylation and exhibits a broad reaction scope and excellent functional group compatibility (>100 examples with up to 96% yield). It also provides a robust formal [2+2+1] cyclization strategy for the concise construction of pyrrolidine skeletons under mild reaction conditions. Mechanistic studies support an inner-sphere single electron transfer pathway for the successful cleavage of inert C-Br bonds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Multidisciplinary Sciences
Shangwen Fang, Jie Han, Chengjian Zhu, Weipeng Li, Jin Xie
Summary: In this study, a gold-catalyzed, four-component reaction was reported, which efficiently breaks a carbon-carbon triple bond and forms four new chemical bonds, achieving the oxo-arylfluorination or oxo-arylalkenylation of internal aromatic or aliphatic alkynes. The site-directing functional groups in the alkynes control the reaction divergence, with phosphonate unit favoring oxo-arylfluorination and carboxylate motif benefiting oxo-arylalkenylation. The reaction proceeds through an Au(I)/Au(III) redox coupling process using Selectfluor as both an oxidant and a fluorinating reagent, resulting in the synthesis of structurally diverse α,α-disubstituted ketones and tri- or tetra-substituted unsaturated ketones with excellent selectivity and yields.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Manuel Freis, Moritz Balkenhohl, David M. Fischer, Tony Georgiev, Roman C. Sarott, Erick M. Carreira
Summary: The cobalt-catalyzed aminocyclization of unsaturated N-acyl sulfonamides in the presence of oxygen was reported, leading to the formation of α- and d-lactam aldehydes. Enantiomerically enriched α- and d-lactam alcohols were obtained by using an optically active cobalt catalyst. The obtained α-lactam aldehydes and alcohols were further elaborated into useful building blocks.
Article
Chemistry, Organic
Manuel Freis, Moritz Balkenhohl, David M. Fischer, Tony Georgiev, Roman C. Sarott, Erick M. Carreira
Summary: This paper reports a cobalt-catalyzed aminocyclization of unsaturated N-acyl sulfonamides in the presence of oxygen, leading to α- and d-lactam aldehydes. Chiral cobalt catalysts were utilized to obtain enantiomerically enriched α- and d-lactam alcohols. The α-lactam aldehydes and alcohols obtained can be elaborated into useful building blocks.
Article
Chemistry, Multidisciplinary
Mariana Zavarize, Nikolai V. V. Sibirev, Yury Berdnikov, Murilo Moreira, Helio T. Obata, Varlei Rodrigues, Vladimir G. G. Dubrovskii, Monica A. Cotta
Summary: InP nanowires were catalyzed by Au, Ag, and Au-Ag nanoparticles on GaAs substrates with different orientations. Statistical analysis and modeling demonstrated that the ratio of droplet surface density to In precursor flux is critical in controlling nanowire growth mode and orientation. These findings enhance our understanding of planar nanowire vapor-liquid-solid growth and provide tools for controlling III-V nanowire growth on lattice-mismatched substrates.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Organic
Matthew R. Nelli, Rachel L. Cantrell, Ryan E. Looper
Summary: A successful gold-catalyzed hydroamination of yneamide tethered amines revealed strategies to access the 1,4-diazepindiones heterocyclic core of the TAN-1057 family of natural products. The precursor amino-yneamides, derived from easily accessible 1,2-diamines and alkynoic acids, are efficiently cyclized to the corresponding diazepineones.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Shang-Fu Yuan, Zong-Jie Guan, Quan-Ming Wang
Summary: The identification of the authentic active species in cluster catalysis is challenging, and the direct structural evidence is valuable but difficult to obtain. In this study, two isostructural clusters were isolated and characterized, showing different catalytic activities and providing clear evidence for the modulation of catalytic performance by regulating the oxidation state of metal atoms.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Shashank Shandilya, Manash Protim Gogoi, Shubham Dutta, Akhila K. Sahoo
Summary: Ynamide, a unique species with inherited polarization of nitrogen lone pair electron to triple bond, has been widely used for the development of novel synthetic methods and the construction of unusual N-bearing heterocycles. This review provides an overall scenic view into the gold catalyzed transformation of ynamides, including their reactivity towards various transfer reagents and carbon nucleophiles.
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
Multidisciplinary Sciences
Rafal Zuzak, Iago Pozo, Mads Engelund, Manuel Vilas-Varela, Jose M. Alonso, Enrique Guitian, Dolores Perez, Diego Pena, Szymon Godlewski
Summary: On-surface synthesis is regarded as a promising approach for generating new molecular structures, particularly successful in the synthesis of graphene nanoribbons and nanographenes. This method combines solution chemistry with ultrahigh vacuum surface transformations, and benefits from the development of characterization techniques.
JOVE-JOURNAL OF VISUALIZED EXPERIMENTS
(2021)
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)
Article
Chemistry, Organic
Faiza Diaba, Gisela Trenchs
Summary: The first violet light-mediated synthesis of gamma- and delta-lactams from N-alkenyl trichloroacetamides is reported in this paper. The reactions are conducted in tetrahydrofuran or 2-methyltetrahydrofuran as the sole solvent without catalysts or additives, under non-anhydrous conditions in an air atmosphere where the solvent serves as the radical initiator.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Feroze Hussain, Sajjad Ahmed, Ashiq Hussain Padder, Qazi Naveed Ahmed
Summary: This study reports a novel and efficient one-pot synthesis method for mixed phosphorotrithioates, which does not require supplementary additives and shows broad applicability.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Hyunjin Oh, Ikyon Kim
Summary: A new 1,2,4-triazole-pyrrolo[1,2-a]pyrazine hybrid system, 6-acylpyrrolo[1,2-a][1,2,4]triazolo[5,1-c]pyrazine, was synthesized using a catalyst-free method. This method involved sequential exposure of pyrrole-2-carbonitrile-derived substrates to DMF-DMA and acyl hydrazide, resulting in the formation of acylated pyrazine and 1,2,4-triazole rings, enabling the installation of various substituents at specific positions on the core skeleton.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Ming Yan, Si-fan Wang, Yong-po Zhang, Jin-zhong Zhao, Zhuo Tang, Guang-xun Li
Summary: Here we developed an efficient photocatalytic approach for the convenient preparation of sulfinamides. The reaction allows for the gram-scale preparation of sulfinamides and the one-pot synthesis of various sulfonyl amides.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Farzaneh Bandehali-Naeini, Zahra Tanbakouchian, Noushin Farajinia-Lehi, Nicolas Mayer, Morteza Shiri, Martin Breugst
Summary: Two tandem catalytic systems were developed for the synthesis of novel 3,4-disubstituted maleimides using the same Ugi adducts. Different maleimide structures can be synthesized using either Pd or Cu catalysis.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Tanya Raghava, Anjan Chattopadhyay, Subhadeep Banerjee, Nivedita Sarkar
Summary: Amine substitution of two ortho fluorine atoms of tetrafluoroterephthalonitrile through SNAr chemistry is easily achievable. But further fluorine substitution is only possible under forcing conditions, yielding valuable fluorophores for bioimaging.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Review
Chemistry, Organic
Anju Chadha, Santosh Kumar Padhi, Selvaraj Stella, Sowmyalakshmi Venkataraman, Thangavelu Saravanan
Summary: Alcohol dehydrogenases are enzymes that use cofactors for oxidation or reduction reactions of alcohols or carbonyl compounds. They are utilized in green chemistry and have applications in the production of pharmaceuticals. Recombinant enzymes have solved the challenge of producing purified enzymes in large quantities. Engineered alcohol dehydrogenases have been used in asymmetric synthesis in industry. Various methods have been established for regenerating expensive cofactors to make the enzymatic process more efficient and economically viable.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
