Article
Chemistry, Multidisciplinary
Matthias Peeters, Jonathan Decaens, Alois Fuerstner
Summary: Chiral [BiRh]-paddlewheel complexes empowered by London dispersion enable the generation of (trifluoromethyl)furfurylidene metal complexes from a bench-stable triftosylhydrazone precursor. These complexes undergo asymmetric [2+1] cycloadditions, providing optically active trifluoromethylated cyclopropane or -cyclopropene derivatives, which are important building blocks for medicinal chemistry and difficult to obtain in optically active form.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Bo-Han Zhu, Cang-Hai Shen, Min-Ling Nie, Fumin Zheng, Chengzhe Huang, Fan Chen, Long Li, Chao Deng, Long-Wu Ye, Peng-Cheng Qian
Summary: In this study, a novel non-noble-metal-catalyzed oxidation/cyclization reaction has been developed to synthesize diversely functionalized lactams in moderate to good yields with excellent diastereoselectivities, without the production of typical cyclopropanation products. Furthermore, the combination with another chemical reaction allows for the high diastereo- and enantioselective synthesis of chiral gamma-lactams containing three contiguous stereocenters. Density functional theory calculations suggest that this reaction possibly involves a carbon cation or proton transfer process.
Article
Chemistry, Organic
Chong -Yang Shi, Tao Han, Feng-Lin Hong, Long-Wu Ye, Qing Sun, Ming-Yu Teng
Summary: A copper-catalyzed oxidative cyclization of alkenyl N-propargyl ynamides is described, which allows for the practical synthesis of diverse spirocyclic gamma-lactams with an exocyclic double bond and high Z/E selectivity in moderate to good yields. Notably, this copper-catalyzed oxidative cyclization demonstrates unique selectivity compared to gold catalysis.
Article
Chemistry, Multidisciplinary
Yizhi Zhang, Gang Zhou, Xingxing Gong, Zhuanzhuan Guo, Xiaotian Qi, Xiao Shen
Summary: In this study, a novel visible-light-induced transition-metal-free cyclopropanation reaction of alkenes was reported. The reaction exhibited high selectivity and was suitable for various alkene substrates, demonstrating its synthetic potential in gram-scale reactions and late-stage functionalization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Wan-Chen Cindy Lee, Duo-Sheng Wang, Congzhe Zhang, Jingjing Xie, Bo Li, X. Peter Zhang
Summary: A catalytic radical process for asymmetric cyclopropanation using Co(II)-based metalloradical catalysis has been developed, enabling the stereoselective synthesis of chiral cyclopropyl alpha-amino acid derivatives with high yields, excellent enantioselectivities, and (Z)-diastereoselectivity. Computational and experimental studies support a stepwise radical mechanism for the reaction, showcasing potential applications in the synthesis of dipeptides.
Article
Chemistry, Organic
Jiupeng Liu, Shuo Tang, Huayan Xu, Ruoyu Zhang, Jingjing Zhao, Puyu Zhang, Pan Li
Summary: A visible-light photocatalytic regioselective [2 + 2 + 1] radical annulation reaction of alkenes, tert-butyl nitrite, and gemdihalides has been developed, providing an efficient and practical approach to obtain isoxazolines in good yields under mild conditions. Gem-dihalides serve as C1 synthons, while cheap tert-butyl nitrite acts as an ideal N-O synthon.
Review
Chemistry, Organic
Guang Ma, Kua-Fei Wei, Man Song, Yu-Li Dang, Yang Yue, Bing Han, Hui Su, Wen-Bo Shen
Summary: Medium-sized organic molecules containing rings, especially seven-membered rings, have significant structural importance. However, accessing these structures is challenging due to entropic effects and transannular interactions. Compared to smaller rings, the synthesis of seven-membered rings is more difficult through traditional cyclization pathways. In recent years, the transition-metal-catalyzed Buchner reaction of alkynes has emerged as an attractive and efficient strategy for synthesizing functionalized seven-membered ring products. This review focuses on the recent progress in this field and provides mechanistic insights, categorized by the type of catalyst used.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Jing Guo, Zi-Sheng Chen, Wen-Shuai Chen, Xin Zhao, Kegong Ji
Summary: A novel P,N-bidentate ligand-assisted gold-catalyzed oxidative amination of beta-amino-ynones has been developed, allowing the simple and efficient construction of various quaternary ammonium-olate salts in good to excellent yields. These unprecedented quaternary ammonium-olate salts can be isolated and purified via simple suction filtration. The broad substrate scope, easy purification, easy further transformation, and mild conditions make it a viable alternative for the synthesis of various quaternary ammonium-olate salts.
Article
Chemistry, Multidisciplinary
Smita Patnaik, Uddhav Kanbur, Arkady Ellern, Aaron D. Sadow
Summary: The study revealed that the (BOXZnR)-B-Ph-Zn-Me2 catalyst can efficiently catalyze the synthesis of silyl ethers and hydrogen under solvent-free conditions. The catalyst adapts its mechanism to achieve the most efficient conversion by adjusting the rate law and experimental rate constants based on reactant concentrations.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Mingxin Liu, Nguyen Le, Christopher Uyeda
Summary: Nickel catalysts promote nucleophilic cyclopropanation reactions using CH2Cl2 as a methylene source and Mn as a stoichiometric reductant. The substrate scope includes a broad range of alkenes bearing electron-withdrawing substituents, and enantioselective cyclopropanations have been developed using chiral PyBox ligands. Mechanistic studies suggest the intermediacy of a (PyBox)Ni=CH2 species and DFT models provide a rationale for the nucleophilic character of the nickel carbene and the sense of enantioinduction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Naho Takemura, Yuto Sumida, Hirohisa Ohmiya
Summary: This article presents a visible-light-driven method for silyl radical generation, which is further enhanced by recent advancements in silylboronate synthesis.
Article
Chemistry, Multidisciplinary
Rachel J. Baker, Justin Ching, Teh Ren Hou, Ivan Franzoni, Mark Lautens
Summary: The dearomatization of 2-naphthols is a simple method for constructing complex 3D structures from simple planar starting materials using rhodium and acid catalysis under mild conditions. The vinyl cyclopropane molecules formed in this reaction exhibit high chemoselectivity and scalability, and can be further functionalized at different sites. Both computational and experimental evidence were used to understand the reaction mechanism.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Guodong Zhang, Chengyu Zhang, Haijun Jiao, Feng Chen
Summary: The compatibility between photogenerated silyl radicals and transition metal catalysis in synthetic organic chemistry remains a challenge. Herein, we present a protocol for photoredox/nickel catalyzed allylic silylation of allyl acetates using a silyl radical intermediate. This method provides a modular synthesis of substituted allylsilanes from silanecarboxylic acids.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Organic
Chong-Yang Shi, Ji-Jia Zhou, Pan Hong, Bo-Han Zhu, Feng-Lin Hong, Peng-Cheng Qian, Qing Sun, Xin Lu, Long-Wu Ye
Summary: An efficient gold-catalyzed cascade cyclization has been developed for the synthesis of tetracyclic gamma-lactams bearing one quaternary carbon center and one tertiary carbon center. The reaction involves alkyne oxidation, carbene-alkyne metathesis, and cyclopropanation, and exhibits moderate to good yields with excellent diastereoselectivities. The proposed mechanistic rationale is well supported by theoretical calculations.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Yun-Xuan Tan, Shijia Li, Lijuan Song, Xinhao Zhang, Yun-Dong Wu, Jianwei Sun
Summary: The first geminal hydroborative cyclization of enynes is disclosed in this study. Unlike known hydroborative cyclizations, this reaction adds hydrogen and boron to the same position, leading to a new reaction mode. By using a specific catalyst, a variety of gem-hydroborated bicyclic products with a cyclopropane unit can be rapidly formed from simple enyne substrates. Control experiments and calculations provide important insights into the reaction mechanism. Notably, two competing pathways may operate, depending on the substrate.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Jesus Gonzalez, Alba de la Fuente, Maria J. Gonzalez, Laura Diez de Tejada, Luis A. Lopez, Ruben Vicente
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2019)
Article
Chemistry, Multidisciplinary
Kota Yamamoto, Enol Lopez, Pablo Barrio, Javier Borge, Luis A. Lopez
CHEMISTRY-A EUROPEAN JOURNAL
(2020)
Review
Chemistry, Multidisciplinary
Ruben Vicente
Summary: This review summarizes key reactivities relying on C-C bond cleavages of cyclopropenes, including both metal-catalyzed and metal-free transformations. The emphasis is on the synthetic utility and mechanistic aspects of various methodologies discussed, covering a range of reactions involving vinyl carbenes, metathesis processes, heterocycles syntheses, SEAr reactions, metalation-ring opening sequences, and cycloadditions. The focus is on results from 2007 to 2019, with relevant pioneering transformations eventually included.
Article
Chemistry, Organic
Olaya Bernardo, Kota Yamamoto, Israel Fernandez, Luis A. Lopez
Summary: This study reports the gold-catalyzed reaction of vinyldiazo compounds and alkenylsilanes to produce skipped dienes, common structural motifs in bioactive compounds. The reaction proceeds with complete regio- and stereoselectivity, with the silyl group serving as a regio- and stereocontrolling element. Additionally, the use of alkynylsilanes as reaction partners yielded skipped enynes through C(sp)-C(sp(3)) coupling.
Article
Chemistry, Multidisciplinary
Olaya Bernardo, Silvia Gonzalez-Pelayo, Israel Fernandez, Luis A. Lopez
Summary: The gold-catalyzed reaction of propargyl esters with alkynylsilanes produces vinylallene derivatives through consecutive [1,2]-acyloxy/[1,2]-silyl rearrangements. This transformation features good yields, full atom-economy, a broad substrate scope, easy scale-up, and low catalyst loadings. The reaction mechanism involves the generation of a gold vinylcarbene intermediate and a type II-Dyotropic rearrangement involving the silyl group and the metal fragment.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Inorganic & Nuclear
[Anonymous]
Summary: This article reviews the recent advances in the synthesis and applications of ferrocene-fused nitrogen heterocycles. The transfer of powerful transition-metal-catalyzed methodologies for C-H bond functionalization of benzene derivatives to ferrocene has played a significant role in this field.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Review
Chemistry, Inorganic & Nuclear
Olaya Bernardo, Silvia Gonzalez-Pelayo, Luis A. Lopez
Summary: The marriage of heterocyclic compounds with ferrocene has been a fruitful field of research, with several ferrocene-embedded heterocyclic compounds reported in recent years. The synergistic combination of properties from both heterocyclic and metallacyclic motifs in fused systems has led to interesting applications, particularly in asymmetric catalysis.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Review
Chemistry, Medicinal
Alba Fombona-Pascual, Javier Fombona, Ruben Vicente
Summary: This research analyzes the development and potential of augmented reality technology in the field of chemistry for three-dimensional molecule visualization. The study finds that there are already some successful examples of augmented reality applications in education and research environments, although traditional two-dimensional screen visualization is still more commonly used for teaching.
JOURNAL OF CHEMICAL INFORMATION AND MODELING
(2022)
Article
Chemistry, Organic
Olaya Bernardo, Javier Gonzalez, Javier Borge, Luis A. Lopez
Summary: In this study, we successfully reported a regioselective synthesis method for silyl-substituted cyclopentadienyl esters through gold-catalyzed migratory cycloisomerization of silyl-substituted vinylallenes. Additionally, we have identified more straightforward synthesis conditions using the multifaceted nature of the gold catalyst, by reacting propargyl esters and alkynylsilanes.
Article
Chemistry, Applied
Patricia Garcia-Martinez, Olaya Bernardo, Javier Borge, Javier Gonzalez, Luis A. Lopez
Summary: The BF3 & sdot;OEt2-catalyzed reaction of azulene with N-protected aziridines provides a general and efficient method for synthesizing phenethylamine-azulene conjugates with high regioselectivity (up to 91% yield). Stereochemical studies and DFT calculations confirm a concerted SN2-type mechanism for the ring-opening reaction of aziridine.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Dario Coto, Iratxe Barbolla, Ruben Vicente
Summary: Silylcyclopropenes as precursors of alpha-silyl vinyl carbenes can undergo reactions with alkenes, leading to the synthesis of cyclopropylsilanes and cis-1,2-disubstituted cyclopropanes with high selectivity.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Ruben Vicente, Eva Tudela, Miguel A. Rodriguez, Angel L. Suarez-Sobrino, Alfredo Ballesteros
Summary: The synthesis of specific cyclopropane-tethered 1,5-enynes, known as 6-alkynyl-4-alkylidenebicyclo[3.1.0]hex-2-enes, led to the discovery of an unprecedented gold-catalyzed rearrangement to indenes. A computational study of the mechanism behind this significant skeleton rearrangement is also presented.
CHEMICAL COMMUNICATIONS
(2022)
Review
Chemistry, Inorganic & Nuclear
Nicola Panza, Giorgio Tseberlidis, Alessandro Caselli, Ruben Vicente
Summary: This article presents an overview of the recent developments in pyridine-containing 12-membered tetraazamacrocycles with pyclen or Py2N2 backbones and their metal complexes from 2017 to the present. It includes the syntheses of newly described ligands and complexes relevant to medicine, as well as the reactivity of complexes bearing these ligands and their applications in catalysis.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Organic
Luis A. Lopez, Javier Gonzalez
ORGANIC & BIOMOLECULAR CHEMISTRY
(2019)