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, Organic
Arben Berisa, Matija Gredicak
Summary: This paper describes the enantioselective reaction between 2,5-disubstituted pyrroles and diaryl-ketimines generated from isoindolinone-derived alcohols. Pyrrole derivatives with a congested tetrasubstituted stereogenic center at the beta-(C3) position are obtained in high yields and enantioselectivities. The reaction can also be extended to 2-monosubstituted pyrroles, producing chiral alpha-(C5) functionalized pyrrole products. Control experiments were conducted to explain the origin of low enantioselectivities in some products.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Samuel G. Meacham, Russell A. Taylor
Summary: A commercial zeolite is an effective heterogeneous catalyst for the Friedel-Crafts alkylation of mandelic acid with aromatic substrates. The reaction proceeds in one step, eliminating the need for inert atmosphere techniques or superacids. The selectivity to mixed diarylacetic acids depends on the zeolite framework, with the FAU framework showing very high selectivity.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Yadav Kacharu Nagare, Imtiyaz Ahmad Shah, Jyothi Yadav, Amol Prakash Pawar, Krishnan Rangan, Rahul Choudhary, Eldhose Iype, Indresh Kumar
Summary: An electrochemical method has been developed to synthesize 2,2-disubstituted indolin-3-ones under mild conditions. A series of nucleophiles have been added to the 2-arylindole-3-ones, generated in situ under metal-free electrochemical oxidative dearomatization of 2-arylindoles, to afford 2,2-disubstituted 3-carbonyl indoles with heteroquaternary centers in 57-79% yields.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Leijie Zhou, Nicola Zanda, Moreshwar Chaudhari, Mariane Felicio Da Silva, Miquel A. . Pericas
Summary: A family of polystyrene-supported ligands based on the design of Defieber and Carreira were developed and successfully applied in the iridium-catalyzed asymmetric allylic amination of unmasked allylic alcohols, resulting in 27 examples with up to 99% enantiomeric excess. Two functional resins, L1 and L4, demonstrated significant advantages including easy preparation, ligand recyclability, and convenient handling for sequential use. Notably, the catalytic use of iridium complexes of L1 and L4 allowed for the efficient reuse of expensive iridium metal, which is not achievable under homogeneous conditions with monomeric complexes.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Song Sun, Zhaobin Wang, Shijia Li, Cong Zhou, Lijuan Song, Hai Huang, Jianwei Sun
Summary: This study presents the first organocatalytic kinetic resolution of unactivated aziridines using sulfur nucleophiles, achieving excellent enantioselectivity. A chiral phosphoric acid was identified as an efficient catalyst for intermolecular ring opening under mild conditions, providing highly enantioenriched beta-amino thioethers and aziridines as useful synthetic building blocks.
Article
Chemistry, Multidisciplinary
Yuanting Huang, Jinyu Tang, Xi Zhao, Yanping Huo, Yang Gao, Xianwei Li, Qian Chen
Summary: The development of P(O)-heteroatom bond-forming reactions is crucial, but previous methods have limitations. This study presents an efficient and green photocatalytic phosphorylation of heteroatom nucleophiles utilizing acid red 51 as the photocatalyst and air as the oxidant under blue LED irradiation. The reaction exhibits broad substrate scope and provides practical access to phosphinic fluorides, phosphinic amides, phosphoramidates, and phosphinates. Mechanistic studies suggest the involvement of a phosphorus-centered radical cation generated by photocatalytic single electron transfer (SET).
Article
Chemistry, Organic
Jake J. Blackner, Deirdre M. Rooney, Joshua W. Hollett, J. Adam McCubbin
Summary: A boronic acid catalyzed carbon-carbon and carbon-nitrogen bond-forming reaction using ferrocenium boronic acid hexafluoroantimonate salt as catalyst has been developed for the functionalization of various pi-activated alcohols. The reaction proceeds under mild conditions and yields up to 98%, with higher yields and selectivity observed when using organosilane nucleophiles. Computational studies provide a mechanistic pathway for the retention of E/Z stereochemistry when using alkenyl silanes as nucleophiles. This methodology is effective with a variety of organosilane nucleophile sub-types, including allylic, vinylic, and propargylic trimethylsilanes.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Letian Zhang, Jiajun He, Jiabin Shen, Hao Xu, Dancheng Zhu, Chao Shen
Summary: A one-pot stepwise Ce(III)/photoassisted cross-dehydrogenative coupling/fluorooxidation process was developed to efficiently construct C3-heteroaryl 3-fluorooxindoles. This method utilized readily available chemical feedstocks and did not require the use of precious metals, oxidants, or additives. The products were obtained in moderate-to-good yields through recrystallization with favorable functional group compatibility. Additionally, this methodology successfully established C-C, C=O, and C-F bonds in a single step, providing a direct transformation of C=C bonds to functionalized C-C bonds.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Liang-Hua Zou, Biao Liu, Cheng Wang, Zeyu Shao, Junqi Zhou, Andong Shao, Jian Wen
Summary: An efficient and green method for synthesizing various alkyl amines through the cleavage of vinylsulfonium salts' C(sp(3))-S bond has been developed. This reaction can be conducted under air atmosphere and shows a broad range of applicability with N-nucleophiles. Additionally, N-vinylazoles can be obtained with moderate to good yields through the reaction of vinylsulfonium salts with N-containing heterocycles in the presence of a base at room temperature.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Rajesh R. Zalte, Alexey A. Festa, Pavel Raspertov, Olga A. Storozhenko, Nikita E. Golantsov, Victor B. Rybakov, Alexey V. Varlamov, Leonid G. Voskressensky
Summary: Interactions between N-(propargyl)indole-2-carbonitriles and nitrogen nucleophiles were investigated in this study. It was observed that reactions promoted by LiHMDS produced mixtures of two product types, depending on the initial attack on either carbon-carbon or carbon-nitrogen triple bonds. By performing the reaction at reduced temperature and with catalytic amounts of LiHMDS, only alkyne hydroamination products were obtained. On the other hand, a one-pot reaction involving N-(propargyl)indole-2-carbonitriles, methanol, and LiHMDS followed by the addition of a nitrogen nucleophile allowed for a selective cyclization sequence toward 1-aminopyrazino-[1,2-a]indoles.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Thorsten Kinsinger, Uli Kazmaier
Summary: The Matteson homologation with vinyl nucleophiles is a versatile tool for synthesizing highly substituted and functionalized allyl boronic esters. It provides high yields and stereoselectivities, especially with sterically demanding alkyl boronic esters and/or Grignard reagents. This method has been successfully applied in the synthesis of the polyketide fragment of lagunamide B.
Review
Chemistry, Multidisciplinary
Xinlan A. F. Cook, Antoine de Gombert, Janette McKnight, Loic R. E. Pantaine, Michael C. Willis
Summary: This review focuses on the methods developed for the challenging coupling of 2-pyridine nucleophiles with (hetero)aryl electrophiles, ranging from traditional cross-coupling processes to alternative nucleophilic reagents and novel main group approaches.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Xi Wang, Youbin Peng, Ling Zhao, Xiaohong Huo, Wanbin Zhang
Summary: Compared to the stereocontrol of the stereocenter at the allyl unit, asymmetric induction of prochiral nucleophiles is a challenging task in Pd-catalyzed asymmetric allylic substitutions due to the remote distance between the chiral catalyst and the prochiral nucleophile. Extensive efforts have been made to address this challenge through the design of chiral ligands. Recently, synergistic catalysis, including bimetallic catalysis and Pd/organocatalysis, has gained attention for its potential advantages in improving reactivity and selectivity, and providing a simple and unified method for the stereocontrol of prochiral nucleophiles. This review summarizes the history and advances in this field.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Organic
Meysam Azizzade, Parviz Rashidi Ranjbar, Akram Sajadi
Summary: A novel regioselective annulation of propargylic alcohols with simple carbazoles has been developed for the synthesis of [3,2,1-jk]carbazole scaffolds. Additionally, in situ synthesis of propargyl alcohols from simple and easily accessible ketones was achieved during the one-pot synthesis of [3,2,1-jk]carbazoles.
Article
Chemistry, Organic
Carlos Sedano, Cintia Virumbrales, Samuel Suarez-Pantiga, Roberto Sanz
Summary: The method proposed in this study can generate 1,2,3-triol fragments through a reaction, with excellent diastereoselectivity, and by overcoming some limitations of the previously reported method, broadens the application scope of polyols.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Organic
Ruben Rubio-Presa, Olaya Garcia-Pedrero, Pablo Lopez-Matanza, Pablo Barrio, Felix Rodriguez
Summary: This method for vicinal dihalogenation of alkenes is simple, efficient, and eco-friendly, utilizing environmentally benign solvents and avoiding purification steps. Pure products are typically obtained through a simple aqueous workup.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
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)
Review
Chemistry, Multidisciplinary
Olaya Garcia-Pedrero, Felix Rodriguez
Summary: Cyclization reactions using cationic intermediates with alkynes as terminating groups offer wide synthetic possibilities, serving as precursors for different functionalities. This type of process shows potential, particularly in the biomimetic synthesis of natural products.
CHEMICAL COMMUNICATIONS
(2022)
Article
Biochemistry & Molecular Biology
Claudia Feberero, Cintia Virumbrales, Carlos Sedano, Lorena Renedo, Samuel Suarez-Pantiga, Roberto Sanz
Summary: A straightforward and transition metal-free one-pot protocol for synthesizing halobenzo[b]furans has been developed using easily available starting materials. The researchers fine-tuned the different steps involved to achieve a successful one-pot procedure and synthesized a wide variety of new halobenzo[b]furans.
Article
Chemistry, Applied
Noelia Velasco, Clara Martinez-Nunez, Manuel A. Fernandez-Rodriguez, Roberto Sanz, Samuel Suarez-Pantiga
Summary: A tandem 1,3-sulfur migration followed by iodocyclization reaction has been developed to synthesize indene-based beta-iodoalkenyl sulfides in the presence of NIS in HFIP. The choice of reaction media is crucial in promoting the reaction, and the proposed mechanism involving NIS activation by HFIP and favoring sulfur migration is supported by experimental evidence. Additionally, the suitability of the synthesized compounds as building blocks for subsequent C-C bond-forming reactions has been demonstrated.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Marta Solas, Samuel Suarez-Pantiga, Roberto Sanz
Summary: This study describes the asymmetric synthesis of cyclopentachromenones from gold-catalyzed reaction of readily available skipped alkenynones. The cascade reaction involves an initial anti-Michael hydroarylation and a subsequent Nazarov cyclization. Excellent enantiomeric ratios and chemical yields are achieved under mild reaction conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Ana Milian, Patricia Garcia-Garcia, Juan J. Vaquero, Roberto Sanz, Manuel A. Fernandez-Rodriguez
Summary: Gold(I)-catalyzed reactions provide a direct route to phenanthrene-based polycycles using external or internal nucleophiles. Alcohols can be used to obtain functionalized dihydrophenanthrenes, while benzo[b]triphenylenes can be synthesized using o-methoxyvinyl-o'-alkynylbiaryls.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Applied
Miguel A. Munoz-Torres, Fernando Martinez-Lara, Marta Solas, Samuel Suarez-Pantiga, Roberto Sanz
Summary: The combination of organolithium chemistry with gold catalysis offers a new synthetic strategy for accessing polysubstituted indoles and carbazoles. This method utilizes ketopyrroles as starting materials and involves a series of reactions to selectively synthesize the desired products.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Cintia Virumbrales, Mahmoud A. E. A. A. A. El-Remaily, Samuel Suarez-Pantiga, Manuel A. Fernandez-Rodriguez, Felix Rodriguez, Roberto Sanz
Summary: This study describes a gold(I)-catalyzed cascade reaction for the stereoselective synthesis of sulfur- or selenium-containing indeno[1,2-b]chromene derivatives, involving a double cyclization process to form polycyclic structures by a proposed key gold-cyclopropyl carbene intermediate.
Article
Chemistry, Applied
Marta Solas, Lorena Renedo, Samuel Suarez-Pantiga, Roberto Sanz
Summary: A gold-catalyzed cascade double cyclization reaction was developed for the synthesis of heterobiaryl compounds, such as furanyl and pyrrolyl 2H-chromenes, from readily available starting materials derived from biomass platform molecules. The reaction involves an initial heterocyclodehydration step followed by an alkyne hydroarylation to form the chromene core.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Carlos de la Cruz, Roberto Sanz, Anisley Suarez, Edgar Ventosa, Rebeca Marcilla, Andreas Mavrandonakis
Summary: This article utilizes density functional theory calculations to screen around 100 phenazine derivatives in aqueous media and identifies crucial positions for functionalization with multiple hydroxy groups to design new anolytes. The combination of experimental and computational methods guides the development of a new molecule with a record low reversible redox potential as a potential anolyte for aqueous redox flow batteries.
Article
Materials Science, Multidisciplinary
Ruben Rubio-Presa, Lara Lubian, Mario Borlaf, Edgar Ventosa, Roberto Sanz
Summary: In the presence of traces of oxygen, viologen-derivatives in redox flow batteries undergo accelerated degradation. We have identified the primary degradation mechanism and proposed a cost-effective and efficient method to evaluate the stability of viologen-derivatives in relation to this degradation. Through molecular engineering, we have synthesized a new viologen-derivative with improved stability by introducing an alkylsulfonate chain with a secondary carbon center joined to the N atom.
ACS MATERIALS LETTERS
(2023)
Review
Chemistry, Organic
Samuel Suarez-Pantiga, Roberto Sanz
Summary: Dioxomolybdenum complexes have shown great potential in deoxygenation reactions of various compounds, including sulfoxides, N-O bonds, and nitro functional groups.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
