Article
Chemistry, Organic
Yakun Wang, Shuaifei Wang, Peiyong Qiu, Lizhen Fang, Ke Wang, Yawei Zhang, Conghui Zhang, Ting Zhao
Summary: An efficient and enantioselective alpha-electrophilic difluoromethylation of beta-keto esters has been achieved by phase-transfer catalysis, providing good enantioselectivities and yields with high C/O regioselectivities. The C/O selectivity of beta-keto esters can be easily reversed and controlled, offering a novel and efficient way for introducing chiral C-CF2H groups.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Jianting Ma, Xue Cui, Junyu Xu, Yinfeng Tan, Yan Wang, Xuesong Wang, Youbin Li
Summary: A one-pot strategy using ynamides as coupling reagents has been developed for the formation of alpha-keto amide bonds under extremely mild reaction conditions. Diversely structural alpha-ketoamides were obtained in up to 98% yield for 36 examples. This reaction offers practical coupling procedure, wide functional group tolerance, and extremely mild conditions, with potential applications in synthetic and medicinal chemistry.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Ningbo Li, Yuxin Wang, Shuo Gu, Chuqian Hu, Qian Yang, Zhaohui Jin, Wen-Tao Ouyang, Jie Qiao, Wei-Min He
Summary: A concise and efficient ring-opening difluorination strategy has been developed for the synthesis of highly functionalized hydroxy-containing α,α-difluoro-β-ketoamides. This transition-metal-free synthetic procedure showed good functional group compatibility and attractive practical potential for large-scale synthesis.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Nicholas A. Ahlemeyer, Matthew R. Straub, David M. Leace, Benjamin A. Matz, Vladimir B. Birman
Summary: Several additional examples of cascade cyclizations of alpha, beta-unsaturated thioesters are reported, proceeding via two distinct mechanistic pathways: enantioselective acyl transfer promoted by amidine-based catalysts (ABCs) and a racemic chain mechanism mediated by a thiolate nucleophile.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Katsuki Endo, Daiki Tomon, Satoru Arimitsu
Summary: This paper reports the highly enantioselective alpha-fluorination of both cyclic and acyclic beta-dicarbonyl compounds, achieving yields of 50-99% with excellent enantioselectivity (up to 98% ee). By using beta,beta-diaryl serines as primary amine organocatalysts and adding alkali carbonates (such as Na2CO3 or Li2CO3), the reaction could be conducted with only 1.1 equiv of Selectfluor.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Sanoop P. P. Chandrasekharan, Narendra Kumar Vaishanv, Ruchir Kant, Kishor Mohanan
Summary: A substrate-controlled reactivity switch was observed in the reaction of alpha-fluoro-beta-ketoamides with arynes. Secondary alpha-fluoro-beta-ketoamides reacted to afford alpha-aryl-alpha-fluoroacetamides through arylation/deacylation, while tertiary alpha-fluoro-beta-ketoamides underwent C-C sigma-bond insertion reaction to give 1,2-disubstituted arenes.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Christopher Mairhofer, Victoria Haider, Thomas Bogl, Mario Waser
Summary: The deoxyfluorination of cyclic alpha-hydroxy-beta-ketoesters using DAST reported in this study demonstrates high levels of stereospecificity, resulting in the configurationally inverted alpha-fluoro-beta-ketoesters in high yields under simple operation conditions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Biochemistry & Molecular Biology
Janah Shaya, Lujain Aloum, Chung-Shin Lu, Peter R. Corridon, Abdulrahman Aoudi, Abeer Shunnar, Eman Alefishat, Georg Petroianu
Summary: A systematic theoretical study was conducted to investigate the hydrogen abstraction and hydroxylation reactions of alpha- and beta-pinenes by cytochrome P450 (CYP) enzymes. The results showed that the major reaction products of CYP-catalyzed hydrogen abstraction from beta-pinene were doublet trans (53.4%) and doublet cis (46.1%) radical conformers. The hydroxylation products of alpha pinene released a total of similar to 50 kcal/mol Gibbs free energy. Our study reveals the reaction mechanism and highlights the formation of different conformers in alpha-pinene and beta-pinene molecules.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Applied
Roman Ottenbacher, Vladimir Kurganskiy, Evgenii P. Talsi, Konstantin P. Bryliakov
Summary: In this study, we reported the enantioselective epoxidation of electron-deficient cis- and trans-alpha,beta-unsaturated amides using the environmentally benign oxidant H2O2. The manganese complexes with bis-amino-bis-pyridine and related ligands as catalysts showed high efficiency and excellent chemo- and enantioselectivity. The presence of NH moiety was found to enhance the enantioselectivity and yield of cis-enamides epoxidation significantly.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Zuo Zuo Wu, Tapas Adak, Martin C. Dietl, Tao Wang, Chao Hu, Hongwei Shi, Petra Kraemer, Matthias Rudolph, Frank Rominger, A. Stephen K. Hashmi
Summary: The study presents a novel gold-catalyzed 2-fold reaction of a bromoalkyne with anthranils to produce alpha-ketoamides. This method provides a new synthetic approach for preparing this functional group.
Article
Chemistry, Multidisciplinary
Hu Tian, Hong-Ming Zhang, Liang Yin
Summary: In this article, a copper(I)-catalyzed asymmetric conjugate addition/protonation with selenols and alpha-substituted alpha,beta-unsaturated thioamides is described, which produces a series of chiral selenides with high to excellent enantioselectivity. The reaction shows a broad substrate scope for both selenols and alpha-substituted alpha,beta-unsaturated thioamides. The catalytic system is also successfully used for asymmetric selenation of beta-substituted alpha,beta-unsaturated thioamides. A [Cu-(R,R-P)-TANIAPHOS]-SePh species is identified by Se-77 NMR spectra, with a chemical shift at delta 462 ppm. Furthermore, a {[Cu-(R)-TOL-BINAP]-SePh}(2) species is characterized by X-ray analysis, confirming the formation of Cu-Se bond in the reaction. Finally, the straightforward transformations of the thioamide group to amine and thioester are demonstrated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Tao Yi, Quan Liu, Yue Zhang, Jinhao Huang, Zhigang Zeng, Yunfeng Chen
Summary: A copper-catalyzed cascade reaction was reported for the selective oxidative cleavage of C-C bonds in β-alkyl nitroolefins, followed by oxidative amidation with amines or amides. The reaction showed high selectivity and yielded α-ketoamides with 66-88% yields. Mechanistic studies revealed that the reaction occurred on more electron-rich allylic nitro tautomers originating from the equilibrium of conjugated nitroalkenes.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Shao-Jie Cheng, Gang Wang, Kui Liu, Zhi-Shi Ye
Summary: A palladium-catalyzed regioselective alpha-amino C-H functionalization has been established via the isomerization of alpha,beta-unsaturated carbonyls including esters, ketones, and amides, providing a straightforward access to a wide range of multicyclic compounds with good yields. This transformation exhibits high regioselectivity, excellent functional group tolerance, and scalability.
Article
Chemistry, Multidisciplinary
Xin Qin, Jinhai Zhang, Zhan-Yong Wang, Yimei Song, Yixiao Yang, Wenhai Zhang, Hongxin Liu
Summary: In this study, a aldol/Michael cascade reaction on the beta,gamma-positions of alpha,beta-unsaturated ketones with ketoamides to construct bicyclic lactams via DBU catalysis has been developed. The substrates exhibited high regio- and diastereoselectivities and yielded moderate to good results (32 examples). Control experiments showed that the hydrogen of the amide played a key role.
Article
Chemistry, Applied
Bo Chen, Chang-Sheng Kuai, Jian-Xing Xu, Xiao-Feng Wu
Summary: A Mn(III)-promoted double carbonylation reaction using anilines and alkylborates or Hantzsch esters has been developed for the synthesis of alkyl alpha-ketoamides with excellent selectivity. The method provides a broad range of derivatives in moderate to good yields.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Sara Meninno, Mario Carratu, Jacob Overgaard, Alessandra Lattanzi
Summary: A novel three-step four-transformation approach was developed for the synthesis of highly functionalized 5-amino-3,4-dihydro-2H-pyrrole-2-carboxylic acid esters, delivering amidines bearing three contiguous stereocenters. The entire sequence was carried out using benign solvents and metal-free conditions, demonstrating the synthetic utility of the products at scale-up.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Rosaria Schettini, Massimo Tosolini, Jawad Ur Rehman, Muhammed Raza Shah, Giovanni Pierri, Consiglia Tedesco, Giorgio Della Sala, Francesco De Riccardis, Paolo Tecilla, Irene Izzo
Summary: Two families of hexameric cyclic peptoids with different alkyl side chains were synthesized and their ionophoric activities were studied, showing a preference for Na+ ions and a potential Na+/H+ antiport transport mechanism. X-ray crystallographic studies on linear N-side chain ionophoric cyclic peptoids revealed a tendency to form layered assemblies.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Review
Chemistry, Applied
Sara Meninno, Francesca Franco, Maurizio Benaglia, Alessandra Lattanzi
Summary: Pyrazoleamides have gained attention as reactive and practical surrogates in asymmetric catalysis, particularly in a variety of metal- and organocatalytic transformations. Their relevance has extended to photoredox catalysis and challenging stereoselective bond-forming reactions in recent years.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Sara Meninno, Rosaria Villano, Alessandra Lattanzi
Summary: A mild and convenient protocol using cheap and stable magnesium monoperphthalate (MMPP) as the oxidant was developed for the alpha-hydroxylation of alpha-substituted malonates, beta-ketoesters, and beta-ketoamides. The protocol allows for the synthesis of various compounds in good yields at room temperature.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Chiara Volpe, Sara Meninno, Carlo Crescenzi, Michele Mancinelli, Andrea Mazzanti, Alessandra Lattanzi
Summary: This study demonstrates an enantioselective one-pot catalytic strategy for the synthesis of dihydroquinoxalinones, using a combination of catalysts and intermediates to achieve high enantioselectivity in the formation of medicinally relevant heterocycles. The reusability of the organocatalyst and the mechanistic insights into the DROC process provide valuable information for further development of enantioselective synthesis strategies.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Francesca Franco, Sara Meninno, Jacob Overgaard, Sergio Rossi, Maurizio Benaglia, Alessandra Lattanzi
Summary: An enantioselective synthesis method for functionalized triflones with a quaternary stereocenter has been developed, utilizing the Michael reaction and nucleophilic acyl substitution. The study highlights the potential of the triflinate anion as a leaving group for stereocontrolled postfunctionalizations.
Article
Chemistry, Multidisciplinary
Alessandra Lattanzi
Summary: The development of organocatalysis and the use of Michael addition reaction have greatly contributed to the synthesis of quaternary stereocenters and the preparation of functionalized building blocks. In this account, the authors highlight their achievements in accessing novel heterocycles with quaternary stereocenters, particularly focusing on the use of organocatalysis derived from Cinchona alkaloids. The enantioenriched heterocycles obtained were further manipulated to prepare useful compounds for downstream applications.
Review
Chemistry, Organic
Sara Meninno
Summary: The depletion of finite primary fossil fuels necessitates a transformation in the chemical industry, particularly in the synthesis of added-value chemicals. Shifting from petro-based starting materials to renewable biomass-derived sources is crucial, as is designing greener processes to reduce environmental impact. Organocatalysis provides an opportunity to upgrade biomass-derived platform molecules in line with Green Chemistry principles, and this review highlights recent advancements in this emerging field.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Sara Meninno, Alessandra Lattanzi
Summary: A one-pot multicomponent reaction, involving Knoevenagel reaction, asymmetric epoxidation, and domino ring-opening cyclization, has been developed for the synthesis of 3-aryl/alkyl piperazin-2-ones and morpholin-2-ones. The reaction proceeds in good yields (38-90%) and high enantioselectivity (up to 99% ee), with two out of three steps being catalyzed by a quinine derived urea. The method has also been applied to the enantioselective synthesis of a key intermediate for the antiemetic drug Aprepitant.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Simona De Vita, Sara Meninno, Lucia Capasso, Ester Colarusso, Maria Giovanna Chini, Gianluigi Lauro, Romolo Rinaldi, Annalisa De Cicco, Veronica Sian, Stefania Terracciano, Angela Nebbioso, Alessandra Lattanzi, Giuseppe Bifulco
Summary: In this study, a new series of histone deacetylase inhibitors (HDACi) with a 2-substituted 1,5-benzothiazepine scaffold were developed. The compounds showed potent HDAC inhibitory activity, especially those containing the sulphone moiety. In addition, they demonstrated cytotoxic effects on cancer cell lines and modulated histone acetyl markers.
BIOORGANIC & MEDICINAL CHEMISTRY
(2023)
Article
Chemistry, Organic
Vincenzo Battaglia, Sara Meninno, Alessandra Lattanzi
Summary: In this study, a novel and concise method for the synthesis of the commonly used antiplatelet drug Plavix was developed. Through careful optimization of reaction conditions, a high synthesis yield and selectivity were achieved.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Vincenzo Battaglia, Sara Meninno, Andrea Pellegrini, Andrea Mazzanti, Alessandra Lattanzi
Summary: An operationally simple method, called the Knoevenagel condensation/asymmetric epoxidation/dominoring-opening esterification (DROE) approach, has been developed to access a wide range of (R) and (S)-α-arylglycine esters using a single solvent and reaction vessel. The method involves commercially available aldehydes, phenylsulfonyl acetonitrile, cumyl hydroperoxide, anilines, and readily available Cinchona alkaloid-based catalysts. Density functional theory calculations revealed the significance of cooperative H-bonding interactions in achieving stereocontrol.
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)
