Article
Chemistry, Multidisciplinary
Tingrui Li, Yilitabaier Julaiti, Xiaopeng Wu, Jie Han, Jin Xie
Summary: The gold-catalyzed ring-opening rearrangement of cyclopropenes provides an efficient method for synthesizing polysubstituted naphthols or aryl-substituted furans. The reaction selectivity between naphthols and furans can be switched by using different gold-carbenes or gold-carbocations as catalysts.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Julian Baars, Isabelle Grimm, Dirk Blunk, Joerg-Martin Neudoerfl, Hans-Guenther Schmalz
Summary: A 12-step total synthesis of the natural product dysiherbol A was achieved, revealing the need for revision of the originally proposed structure and absolute configuration. The synthesis involved key steps including Cu-catalyzed addition/enolate-trapping, Au-catalyzed double cyclization, and late installation of the C5-bridgehead methyl group. Spectroscopic measurements confirmed the identity of the synthetic compound with the natural product but with an opposite molecular rotation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Sara Fernandez-Moyano, Guillermo Marcos-Ayuso, Marconi N. Penas-Defrutos, Camino Bartolome, Pablo Espinet
Summary: F-19 NMR monitoring reveals that heating trans-[Au(III)Rf(2)I(2)](-) solutions (Rf = C6F3Cl2-3,5) leads to the formation of cis-[AuRf(2)I(2)](-), [AuRf(3)I](-), and [AuRfI(3)](-) via kinetic competition between isomerization and Rf/I scrambling. The easy reductive elimination of Rf-I from [AuRfI(3)](-) (also forming [AuI2](-)) drives the system evolution, providing faster kinetics than any Rf-Rf couplings from the coexisting species, which hinders the desired thermodynamically preferred C-C coupling. A kinetic model is proposed, where I- dissociation triggers both isomerization and transmetalation steps, which is consistent with the experimental data. DFT calculations support that the lower bond strength of Au-III-I compared to other halides leads to a pathway switch, making C-I coupling kinetically preferred. Therefore, it is advisable to avoid C-I coupling in reactions seeking C-C coupling.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Applied
Fernando Martinez-Lara, Anisley Suarez, Noelia Velasco, Samuel Suarez-Pantiga, Roberto Sanz
Summary: The gold-catalyzed transformation of propargylic glycols with thiols results in the formation of alpha-indol-3-yl alpha-((Z)-2-thioalkenyl) ketones through a complex but selective reaction mechanism. This sequence involves regioselective thiolation of indolyl diols followed by the attack of sulfur on the activated alkyne, rather than the indole. The final compounds are obtained in high yields from simple starting materials such as indolyl acyloins, ethynyl magnesium bromide, and thiols.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Cui-Cui Li, Siqi Zhang, Jian Tang, Ruijun Jian, Yu Xia, Liang Zhao
Summary: This study develops a two-step synthetic method to achieve three unprecedented aryl dicarbanion-bonded Ag-13 nanoclusters using protective macrocyclic ligands. The research not only reveals the formation and evolution process of cluster species in catalytic reactions but also discovers novel inter- and intra-cluster coupling steps.
Article
Chemistry, Applied
Ali Wang, Xiaoping Hu, Xin Xie, Yuanhong Liu
Summary: A gold-catalyzed cyclization/cascade skeletal rearrangement of o-cyanophenylalkynones with 3-amino-benzo[d]-isoxazoles has been developed, providing an approach for synthesizing medium-sized benzolactones. Nucleophilic attack preferentially occurs at the keto moiety instead of the gold-carbene, initiating an attractive cascade process involving carbene transfer, 1,2-aryl migration, cycloaddition, and ring-expansion resulting in multiple bonds cleavage of the initial substrates.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Physical
Sebastiano Campisi, Marta Stucchi, Nikolaos Dimitratos, Alberto Villa
Summary: This article celebrates Laura Prati's long and successful scientific career, highlighting her major accomplishments in inorganic chemistry since she began her work as a researcher. She made significant contributions in the field of catalyst synthesis, particularly in the development of innovative strategies for preparing catalysts and the colloidal synthesis of metal nanoparticles, mainly gold. Her investigations in colloids for catalysis had a profound impact on catalyst synthesis and optimization. Throughout her career, she also focused on liquid-phase oxidation reactions, biomass valorization processes, and hydrogenation and hydrogenolysis reactions. Her discoveries have greatly influenced researchers in the fields of heterogeneous catalysis and material design.
Article
Chemistry, Physical
Sebastiano Campisi, Marta Stucchi, Nikolaos Dimitratos, Alberto Villa
Summary: This account highlights Laura Prati's significant contributions to the field of inorganic chemistry, particularly in the area of liquid-phase heterogeneous catalysis. Her innovative approaches to catalyst synthesis, particularly in the colloidal synthesis of metal nanoparticles, have greatly influenced the design of materials. Additionally, her investigations into oxidation and valorization processes have expanded knowledge in biomass conversion.
Article
Chemistry, Multidisciplinary
Meng-Ying Hao, Yin Zhang, Na Lin, Rong Fu, Xiao-Shuang Ji, Bo Jiang, Shu-Jiang Tu, Wen-Juan Hao
Summary: A new gold(i) self-relay catalysis reaction has been reported, which enables the annulative oxygenation of propargylic alcohols with various O-nucleophiles, producing functionalized benzofurans in moderate to good yields under mild conditions. This protocol boasts the pi- and sigma-Lewis acid capability of gold complexes, showcasing high molecular convergence, broad substrate flexibility, high functional group compatibility, and mild conditions.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Applied
Camille Van Wesemael, Nicolas Brach, Mihaela Gulea, Gaelle Blond
Summary: A series of 3-allenyl benzo[b]thiophenes were synthesized through a gold(I)-catalyzed domino reaction. The process involves a 5-endo-dig cyclization with C S bond formation and consecutive S-to-C propargyl migration via [3,3]-sigmatropic Claisen rearrangement. Various fused O-heterocycles can be obtained from a substrate bearing a 3-butynol moiety via intramolecular hydroalkoxylation. The gold-mediated 1,3-migration involving allenyl to propargyl rearrangement is also described.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Jing Liu, Yusheng Yang, Weiming Shi, Zhi-Xiang Yu
Summary: We present computational evidence for a metalla-Claisen rearrangement (MCR) in the gold-catalyzed [4+2] cycloaddition reaction of yne-dienes. The reaction proceeds through exo cyclopropanation, followed by MCR and reductive elimination. The presence of a cyclopropane moiety formed in the initial step greatly facilitates the MCR process. Additionally, we explore the significance of the combination of tether group and terminal substituent on alkyne in the yne-diene substrates. We also investigate whether an MCR mechanism is involved in the rhodium-catalyzed [4+2] reaction of yne-dienes. These findings and insights represent a significant advancement in the field of catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Kevin Bevernaege, Nikolaos V. Tzouras, Albert Poater, Luigi Cavallo, Steven P. Nolan, Fady Nahra, Johan M. Winne
Summary: Triazolinediones are highly reactive dienophiles that can act as electrophilic amination reagents towards enolisable C-H bonds or weak C-H bonds. This reactivity can be significantly enhanced via gold(i)-catalysis, resulting in successful benzylic C-H aminations under mild conditions. The observed selectivity patterns and mechanistic rationale suggest a novel pathway for triazolinedione-induced aminations.
Article
Chemistry, Multidisciplinary
Ashley J. Basson, Mark G. McLaughlin
Summary: The transformation reported is a sustainable, modular, rapid, and high-yielding method for synthesizing densely functionalized 5-aminooxazoles and thiazoles. It is tolerant to a wide range of functional groups and is typically complete in under 30 minutes. The process is environmentally friendly due to the choice of catalyst and solvent, as well as the production of benign alcoholic by-products.
Article
Chemistry, Organic
Xiaoshuo Wang, Shubing Shu, Xiaojing Wang, Renshi Luo, Xiayi Ming, Tao Wang, Zhenming Zhang
Summary: A facile electrochemical method has been developed for the sulfonylative cycloether-ification of unsaturated alcohols and acids, utilizing sulfonyl hydrazides. The reaction proceeds via electro-oxidation, radical addition, and intramolecular oxygen nucleophilic process. This methodology demonstrates broad substrate scope and good functional group compatibility, providing a valuable synthetic tool for the formation of oxygen heterocycles. Control experiments indicate that the N-H bonds of sulfonyl hydrazide are non-essential.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Marina Velado, Manuel Martinovic, Ines Alonso, Mariola Tortosa, Roberto Fernandez de la Pradilla, Alma Viso
Summary: The base-induced [2,3]-sigmatropic rearrangement of enantiopure 2-sulfinyl dienes has been optimized using NaH and iPrOH. The reaction proceeds through allylic deprotonation and sulfoxide-sulfenate rearrangement. The presence of a terminal allylic alcohol is crucial for achieving complete regioselectivity and high enantioselectivities.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Fuying Zhu, Yamei Lin
Summary: In this study, a low-metal iron-supported catalyst (Fe20/NC-Mg) was reported for the efficient synthesis of quinoxaline compounds, using water as a solvent and without additional bases. The synergistic effect of FeNx site and Mg (OH)2 nanorods in the catalyst played a key role in achieving high yields (82-91%) in 16 examples. The gram-level synthesis and reusability of the catalysts after four cycles demonstrated its industrial application potential.
Article
Chemistry, Organic
Mikhail Kozlov, Alexey Tyurin, Andrey Dmitrenok, Vyacheslav Rusak, Aleksander Fedorov, Igor Zavarzin, Yulia Volkova
Summary: This study presents a novel and practical synthesis method for phosphorus-substituted 1,3,4-thiadiazolines using phosphorylthioformic acid hydrazides and ketones. The protocol demonstrates operational simplicity, availability of reagents, and tolerance towards different functional groups.
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.
