Article
Chemistry, Organic
Anton S. Makarov, Arthur N. Bakiev, Diana A. Eshmemeteva
Summary: We present a metal- and additive-free method for synthesizing meta-substituted anilines using commercially available or one-step accessible substituted methylvinyl ketones, N-acylpyridinium salts, and primary/secondary alkyl- and arylamines. This method enables the synthesis of anilines with uncommon substitution patterns and has potential applications in medicinal chemistry and materials science.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Fangling Lu, Kan Zhang, Yanxiu Yao, Ying Yin, Jiafu Chen, Xinwei Zhang, Yin Wang, Lijun Lu, Ziwei Gao, Aiwen Lei
Summary: A highly stereoselective synthesis of thiocyanated enaminones was achieved through an electrochemical process, with up to 87% yields. The transformation proceeded smoothly without the need for external oxidants, electrolytes, or transition-metal catalysts, showcasing its potential for practical application.
Article
Chemistry, Organic
Hao-Dong Tian, Zi-Hao Fu, Chen Li, Huang-Chu Lin, Ming Li, Shao-Fei Ni, Li-Rong Wen, Lin-Bao Zhang
Summary: An efficient electrochemical synthesis of sulfonated phenanthrenes via the reaction of internal alkynes with sulfonyl hydrazides has been established. This method does not require metal catalysts or external oxidants, providing a green and mild route to functionalized phenanthrenes.
Article
Chemistry, Organic
Ying Wang, Ning Xu, Weiwei Li, Jiaojiao Li, Yijun Huo, Wenrong Zhu, Qiang Liu
Summary: An efficient electrochemical method has been developed for the direct synthesis of complicated 1,3-diselenyl-dihydroisobenzofurans from substituted o-divinylbenzenes and diselenides under external oxidant free conditions at room temperature. A radical mechanism is proposed for this novel and practical transformation.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Jian-Qiang Zhao, Xue-Man Zhang, Yu-Ying He, Qiao-Qiao Peng, Han-Wen Rao, Yan-Ping Zhang, Zhen-Hua Wang, Yong You, Wei-Cheng Yuan
Summary: This study describes an organocatalytic asymmetric [3 + 2] cyclo-addition of beta-trifluoromethyl enones with 3-(N-2,2,2-trifluoroethyl) benzothiophene ketimines and 2-(N-2,2,2-trifluoroethyl) benzothiophene ketimines for the first time. A wide range of vicinally bis(trifluoromethyl)-substituted spiro pyrrolidine-benzothiophenones were obtained with excellent stereocontrol, including those with four contiguous stereocenters in the spirocyclic benzothiophenone moiety.
Article
Chemistry, Organic
Chuan-Jin Hou, Alexander W. Schuppe, James Levi Knippel, Anton Z. Ni, Stephen L. Buchwald
Summary: A method for stereoselective hydroalkenylation of alkynes using enol triflates was reported in this study. The formation of Z,Z- or Z,E-1,3-dienes with excellent stereoselectivity and yield was achieved by leveraging an in situ-generated and geometrically pure vinyl-Cu(I) species. This approach allowed for the synthesis of highly substituted Z-dienes, including pentasubstituted 1,3-dienes, which are challenging to prepare using existing methods.
Article
Chemistry, Multidisciplinary
Kaixia Sui, Yuting Leng, Yangjie Wu
Summary: A highly efficient method for synthesizing difluoroarymethyl-substituted benzimidazo[2,1-a]isoquinolin-6(5H)-ones was developed using 2-arylbenzoimidazoles with alpha,alpha-difluorophenylacetic acid as reaction substrates through radical cascade cyclization. The strategy offers excellent functional group tolerance and enables the generation of the desired products in good yields under base- and metal-free conditions.
Article
Chemistry, Organic
Jian-Qiang Chen, Xiangxiang Luo, Meiling Chen, Yi Chen, Jie Wu
Summary: A novel alkoxycarbonyl-radical-triggered cascade cyclization of 1,7-enynes, with alkyloxalyl chlorides as the ester units, for the synthesis of benzo[j]phenanthridines is reported. The reaction conditions are compatible with a broad range of alkoxycarbonyl radical sources and enable the installation of an ester group in the polycyclic compound. This radical cascade cyclization reaction exhibits excellent functional group tolerance, mild reaction conditions, and good to excellent yields.
Article
Chemistry, Organic
Jie Shi, Li-Yun Guo, Qu-Ping Hu, Yu-Tao Liu, Qing Li, Fei Pan
Summary: A photoredox-catalyzed radical cascade reaction has been developed for the synthesis of lactam-substituted gem-difluoroalkenes, providing a simple method with good functional group tolerance and high yields.
Article
Chemistry, Organic
Zengqiang Feng, Baoxiang Zhu, Bingbing Dong, Li Cheng, Yunpu Li, Zechao Wang, Junliang Wu
Summary: An efficient and novel visible-light-promoted radical difluoromethylation method for synthesizing alpha-CF2H-substituted ketones has been described in this study. Various alpha-CF2H-substituted ketones are successfully created based on a SET process, providing a simple and operationally straightforward method with broad functional group compatibility.
Article
Chemistry, Multidisciplinary
Yue Cui, Siyu Li, Hesheng Wang, Jing Zeng, Yichen Wang, Xiubin Bu, Xiaobo Yang, Zhen Zhao
Summary: In this study, a regioselective Rh(III)-catalyzed strategy was developed for C-H bond naphthylation using aryl imidates and oxa bicyclic alkenes, resulting in the synthesis of diverse naphthalene-substituted aromatic esters. The possibility of further functionalization and derivatization of C-H bonds is achieved through the cascade directing group transformation into ester.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Shihao Li, Chenglong Zheng, Sheng Wang, Xiao-Xuan Li, Qi Zhang, Shilu Fan, Yi-Si Feng
Summary: A novel three-component alpha-acylated difunctionalization strategy has been developed using a direct hydrogen atom transfer process of photoinduced acyl azolium salts. Various olefins can be directly converted into ketone derivatives, including 1,4-dione, beta-silyl ketone, 1,5-dione, etc., with simple irradiation without the need for a catalyst.
Letter
Chemistry, Organic
Nicholas J. Venditto, Jeffrey A. Boerth
Summary: Multicomponent radical polar crossover (RPC) reactions are powerful tools for efficient synthesis of molecules with high complexity. However, little research has been done on multicomponent RPC reactions using carbonyl pi-bond electrophiles. In this study, a mild and photoredox-catalyzed decarboxylative multicomponent RPC reaction was developed to synthesize diverse gamma-amino butyric acid derivatives. This reaction also enables the synthesis of complex and biologically relevant gamma-lactam compounds.
Article
Chemistry, Multidisciplinary
Ransong Ma, Zhoubin Deng, Ke-Hu Wang, Junjiao Wang, Danfeng Huang, Yingpeng Su, Yulai Hu, Xiaobo Lv
Summary: An efficient and novel photoinduced trifluoromethylation using CF3Br as a trifluoromethyl source is described. With commercially accessible fac-Ir(III)(ppy)3 as the catalyst, successful radical trifluoromethylation between O-silyl enol ether and CF3Br occurs. This method provides various alpha-CF3-substituted ketones with a broad substrate scope in good yields under mild reaction conditions.
Review
Chemistry, Multidisciplinary
Zhifeng Zhang, Yang Chen, Xiao Gu, Chun-Yu Ho
Summary: Well-controlled olefin insertion is crucial for achieving efficient and selective bulk and fine-chemical synthesis. Nickel catalysts, particularly those based on N-heterocyclic carbene (NHC) ligands, have shown great potential in meeting the diverse demands of olefin codimerization and hydrovinylation. These catalysts offer a high level of control and have the ability to unite previously unreactive substrate pairs, leading to the synthesis of complex and structurally diverse compounds.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Organic
Elena Petit, Llufs Bosch, Anna M. Costa, Jaume Vilarrasa
JOURNAL OF ORGANIC CHEMISTRY
(2019)
Article
Chemistry, Organic
Victor Cascales, Hector Carneros, Alejandro Castro-Alvarez, Anna M. Costa, Jaume Vilarrasa
Summary: Chiral nitroalkenes were utilized for the Michael additions of aldehydes for the first time, catalyzed by pyrrolidine derivatives. The asymmetric induction with (S)-proline or (R)-proline was observed, but was limited by the steric hindrance of the catalysts. Nitrocyclobutane intermediates were frequently formed, which were more stable compared to those from (E)-1-nitro-2-phenylethene. The cyclobutanes and final products were characterized using 2D NMR and chemical correlations.
Article
Chemistry, Medicinal
Elena Petit, Lluis Bosch, Anna M. Costa, Ignacio Rodriguez-Izquierdo, Daniel Sepulveda-Crespo, M. Angeles Munoz-Fernandez, Jaume Vilarrasa
Summary: In this study, novel amides with aliphatic chains located at the C7 position of the indole ring were synthesized for potential vaginal microbicides. These compounds, when combined with polyols decorated with complementary click partners, showed no cytotoxicity and retained activity against HIV-1, indicating a promising approach for developing 4th generation entry inhibitors.
Article
Chemistry, Organic
Anna M. Costa, Lluis Bosch, Elena Petit, Jaume Vilarrasa
Summary: A computational study was conducted on a series of Michael acceptors as potential alternatives to maleimides for linking cytotoxic drugs with mAbs. The study showed that methanethiol reacts more rapidly with maleimides than with ethynephosphonamidates and propynamides, in agreement with experimental results.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Lucy van Dijk, Ruchuta Ardkhean, Mireia Sidera, Sedef Karabiyikoglu, Ozlem Sari, Timothy D. W. Claridge, Guy C. Lloyd-Jones, Robert S. Paton, Stephen P. Fletcher
Summary: The study proposes a catalytic cycle for the highly enantioselective Suzuki-Miyaura coupling of boronic acids and racemic allyl halides catalyzed by Rh(i), and reveals the reaction mechanism through kinetic isotope effects and experiments with stable substrates. The findings suggest that the high enantioselectivity is attributed to a common Rh complex formed from both allyl halide enantiomers.
Article
Chemistry, Multidisciplinary
F. Wieland Goetzke, Mireia Sidera, Stephen P. Fletcher
Summary: In this study, a novel Rh-catalyzed reaction was reported for the synthesis of chiral, substituted cyclobutanes using asymmetric hydrometallation with salicylaldehydes, enabling subsequent transformations. This has significant implications for the asymmetric synthesis of cyclobutenes.
Correction
Chemistry, Multidisciplinary
F. Wieland Goetzke, Mireia Sidera, Stephen P. Fletcher
Summary: The paper corrects the study on the catalytic asymmetric hydrometallation of cyclobutenes with salicylaldehydes by F. Wieland Goetzke et al., published in Chem. Sci., 2022, DOI: 10.1039/d1sc06035j.
Article
Chemistry, Multidisciplinary
Anna M. Costa, Victor Cascales, Alejandro Castro-Alvarez, Jaume Vilarrasa
Summary: This study computationally examines the tendency of carbonyl compounds to form Iminium ions by reacting with pyrrolidine or chiral pyrrolidine derivatives. The results show that the relative energy can be used to predict the predominant formation of iminium species. In amino-catalyzed reactions, the efficiency and conversion rate depend on the relative energy of the iminium intermediates.
Article
Chemistry, Organic
Anna M. Costa, Alejandro Castro-Alvarez, Daniel Fillot, Jaume Vilarrasa
Summary: The energies of the CH2=CH-CH=N+R2 + HNR*(2) + CH2=CH-CH=N+R*(2) + HNR2 reactions and similar equilibria with cinnamaldehyde have been calculated and compared. The predicted order of stability of the iminium ions in very polar solvents differed from that in the gas phase. These findings can help predict the dominant iminium salts formed when conjugated carbonyl compounds are reacted with secondary amines and appropriate acids.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Anna Maria Costa, Nuria Escaja, Carles Fite, Miguel Gonzalez, Sergio Madurga, Elisabet Fuguet
Summary: The University of Barcelona has applied problem-based learning (PBL) methodology in chemistry courses to determine the relevant factors for satisfactory application of this approach in different contexts. Due to the COVID-19 pandemic, the methodology had to be adapted to an online version, and a comparative study identified key aspects that contribute to PBL's successful application. Overall, using Moodle and BBCollaborate as live teaching platforms has a positive impact on student learning and satisfaction. Despite a preference for face-to-face implementation, online PBL is evaluated positively compared to traditional online teaching, thanks to PBL's intrinsic characteristics that enhance learning motivation and facilitate collaborative work.
JOURNAL OF CHEMICAL EDUCATION
(2023)
Article
Chemistry, Organic
Miguel Mellado-Hidalgo, Elias A. Romero-Cavagnaro, Sajanthanaa Nageswaran, Sabrina Puddu, Stuart C. D. Kennington, Anna M. Costa, Pedro Romea, Felix Urpi, Gabriel Aullon, Merce Font-Bardia
Summary: A direct and asymmetric syn-aldol reaction between N-acyl-1,3-oxazinane-2-thiones and dialkyl acetals from aromatic acetals has been developed, using 2-5 mol % [DTBM-SEGPHOS]NiCl2, TMSOTf, and lutidine as catalysts. The oxazinanethione heterocycle, used for the first time in asymmetric carbon-carbon bond-forming reactions, can be smoothly removed to provide access to a variety of enantiomerically pure compounds with high synthetic value.
Review
Biochemistry & Molecular Biology
Anna M. Costa
Summary: Amphidinolides are a diverse family of macrolides isolated from dinoflagellates, displaying varying cytotoxicity. Despite their potential as anticancer agents, their full bioactivity and mode of action remain unclear due to limited access to samples. Only five amphidinolides have been studied, all of which interact with actin, a vital cytoskeletal protein. This review focuses on actin-interacting amphidinolides, discussing their destabilizing or stabilizing effects on F-actin and suggesting further research is needed for a better understanding of this interaction.
