Article
Chemistry, Multidisciplinary
Beatriz Gonzalez-Saiz, Pablo Pertejo, Pablo Pena-Calleja, Marcin Mielczarek, Tomas Hermosilla, Israel Carreira-Barral, Olivia de Miguel, Francisco Rodriguez-Vidal, Roberto Quesada, Maria Garcia-Valverde
Summary: The selection of the appropriate base in Ugi/post-condensation sequences allows for the selective synthesis of functionalized lactams with different ring sizes. The developed methodology uses inexpensive bases under mild and non-sensitive conditions, resulting in the easy generation of molecular diversity from simple synthons.
Article
Biochemistry & Molecular Biology
Rickard Lindroth, Hogan P. Bryce-Rogers, Thomas P. M. Merke, Carl-Johan Wallentin
Summary: This study presents a highly efficient one-pot procedure for the direct oxidation of aldehydes to esters mediated by visible-light. By utilizing a combination of indium triflate and N-bromosuccinimide, NBS, with either ortho-esters or alcohols, rapid access to a variety of esters can be achieved.
PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES
(2022)
Article
Chemistry, Organic
Paula Oroz, Claudio D. Navo, Alberto Avenoza, Jesus H. Busto, Francisco Corzana, Gonzalo Jimenez-Oses, Jesus M. Peregrina
Summary: The study introduces a novel method for the chemo- and diastereoselective 1,4-conjugate additions of Se-nucleophiles to a chiral bicyclic dehydroalanine, offering a promising route for the synthesis of enantiomerically pure selenocysteine derivatives with high potential for chemical biology applications.
Article
Chemistry, Organic
Jie Li, Pei Zhao, Ruoling Li, Wen Yang, Wanxiang Zhao
Summary: An efficient rhodium-catalyzed beta-dehydroborylation of aldehyde-derived silyl enol ethers with bis(pinacolato)diboron is described, leading to a wide array of valuable functionalized beta-boryl silyl enolates with high efficiency and excellent stereoselectivity. The borylated products can be readily converted into diverse synthetically useful molecules through versatile carbon-boron bond transformations.
Article
Chemistry, Multidisciplinary
Shuang Zhao, Yi He, Feiyu Gao, Yue Wei, Jiawei Zhang, Mengxiao Chen, Yunyun Gao, Yuan Zhang, Jun-Yan Liu, Zufeng Guo, Zhenghua Li, Shenyou Nie
Summary: A highly efficient one-pot base-promoted post-Ugi 5-exo-dig Conia-ene-type cyclization method has been developed for the synthesis of diverse 2,2-disubstituted 3-methyleneindoline derivatives. Mechanistic studies suggest that an intramolecular hydrogen bond plays a crucial role in this process. The antiproliferative evaluation of cancer cell lines demonstrates the practical utility of this protocol for the green synthesis of bioactive compound libraries.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Applied
Ming Li, Yunfeng Cui, Zefei Xu, Xi Chen, Jinhui Feng, Min Wang, Peiyuan Yao, Qiaqing Wu, Dunming Zhu
Summary: This study presents an enzymatic cascade reaction for the efficient synthesis of chiral intermediates with alpha,gamma-stereogenic centers, providing a new route for the synthesis of various bioactive compounds.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Organic
Preety Saini, S. S. Bari, Shalu Thakur, Ankita Garg, Sandeep Kumar, Sanjay K. Mandal, Aman Bhalla
Summary: This study describes the synthesis of novel ortho-, meta- and para-(2-benzo[d]oxazolyl)phenyl-beta-lactams 5 using isomeric (ortho-, meta- and para-) (2-beno[d]oxazolyl)phenyl Schiff bases 4. The formation of trans configured beta-lactams 5 using O-alkyl/O-aryl substituted acids has been investigated. The relative trans configuration of the C-3 and C-4 protons in products 5 was examined using coupling constant values. Characterization of the synthesized products was done using various spectroscopic techniques.
SYNTHETIC COMMUNICATIONS
(2022)
Article
Chemistry, Applied
Chen Xu, Chao Ning, Song Yang, Yin Wei, Min Shi
Summary: An effective and atom-economical method to synthesize enantiomerically enriched cyclic beta-amino alcohols via a rhodium-catalyzed asymmetric cycloisomerization has been reported. The reactions proceed through a Rh-catalyzed transformation that allows the generation of a range of enantiomerically enriched cyclic beta-amino alcohols tethered to an alkene and an 1,3-dione moiety in good yields with high ee values. Additional derivatizations were also carried out, including allylation and RCM reaction, as well as the preparation of a pyrazole derivative.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Quan Gou, Binfang Yuan, Man Ran, Jian Ren, Ming-Zhong Zhang, Xiaoping Tan, Tengrui Yuan, Xing Zhang
Summary: With the assistance of a practical directing group (COAQ), the first catalytic protocol for the palladium-catalyzed C(sp(3))-H monoarylation of methanol has been developed, providing an invaluable synthesis means to establish extensive derivatives of crucial arylmethanol functional fragments. The gram-scale reaction, broad substrate scope, excellent functional group compatibility, and even the practical synthesis of medicines further demonstrate the usefulness of this strategy.
Article
Chemistry, Physical
Alina K. Bakunova, Tatiana Y. Isaikina, Vladimir O. Popov, Ekaterina Yu. Bezsudnova
Summary: D-amino acids are valuable building blocks for the synthesis of biologically active compounds and pharmaceuticals. The efficient asymmetric synthesis of optically pure D-amino acids using a pyridoxal-5'-phosphate-dependent transaminase from Haliscomenobacter hydrossis was investigated. A one-pot three-enzyme system was constructed, achieving high product yield and enantiomeric excess. Factors such as high concentration of alpha-keto acids and low reaction temperature were found to reduce cofactor leakage and increase stability of the transaminase.
Article
Chemistry, Multidisciplinary
Takeru Miyakoshi, Nadja E. Niggli, Olivier Baudoin
Summary: In the past years, Pd-0-catalyzed C(sp(3))-H activation has provided efficient and economical methods for synthesizing carbo- and heterocycles via direct C(sp(2))-C(sp(3)) bond formation. This study reports a 1,4-Pd shift that enables the synthesis of N-heterocycles, which are difficult to build through direct reactions. The reaction involves the 1,4-Pd shift of o-bromo-N-methylanilines at the N-methyl group, followed by intramolecular trapping and remote C-C bond formation, resulting in the formation of biologically relevant isoindolines and beta-lactams. The selectivity of the reaction is influenced by the choice of ligand, with NHCs favoring the formation of products through remote C-C coupling.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Sushobhan Chowdhury, Gunjan Chauhan, Ajay Kumar, Bipin Chaturvedi, Chinmaya Behera
Summary: Gamma- and delta-lactams are important structural motifs found in various natural products, biologically active molecules, and functional materials. This study presents a simple and high-yielding synthesis method for the preparation of diverse N-aryl gamma- and delta-lactams from inexpensive starting materials.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Medicinal
Nuno Guerreiro Alves, Ines Bartolo, Americo J. S. Alves, Diana Fontinha, Denise Francisco, Susana M. M. Lopes, Maria I. L. Soares, Carlos J. Simoes, Miguel Prudencio, Nuno Taveira, Teresa M. V. D. Pinho e Melo
Summary: The newly synthesized spiro-beta-lactams demonstrated significant anti-HIV-1 activity in vitro and promising inhibitory effects on both the hepatic and blood stages of Plasmodium infection.
EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY
(2021)
Article
Chemistry, Organic
Uladzimir S. Masiuk, Yaroslav V. Faletrov, Dzmitry G. Kananovich, Iryna Mineyeva
Summary: The stereodivergent synthesis of cis- and trans-2,6-disubstituted tetrahydropyrans (THPs) has been achieved through the oxa-Michael cyclization of (E)-zeta-hydroxy alpha,beta- unsaturated esters promoted by sodium hexamethyldisilazide. The reaction at low temperature (-78 degrees C) yields the thermodynamically favored trans-THPs with high stereoselectivity, while the reaction at room temperature does not produce the desired cis-THPs as major products and has poor stereocontrol. The addition of tetramethylethylenediamine significantly improves the stereochemical outcome of the room-temperature cyclization and allows for high cis-selectivity.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Lei Chen, Mi Zhou, Lin Shen, Xiaochun He, Xiong Li, Xuemei Zhang, Zhong Lian
Summary: A metal- and base-free method for the C(sp(2))-H arylation of secondary and tertiary enamides with aryldiazonium salts and ex situ generated SO2 has been developed. This approach produces beta-amidovinyi sulfones with excellent stereoselectivities in moderate to excellent yields, showcasing good functional group tolerance and environmentally benign reaction conditions. Mechanistic experiments suggest that this sulfonylation proceeds via a radical pathway.
Article
Multidisciplinary Sciences
Monica Fiorenza Boselli, Chiara Faverio, Elisabetta Massolo, Laura Raimondi, Alessandra Puglisi, Maurizio Benaglia
Summary: The development of new methods for introducing fluorine atoms or fluorinated moieties in molecular scaffolds is crucial in organic synthesis. The incorporation of the SCF3 group into organic molecules has shown beneficial effects on drug stability and bioavailability. By using a chiral auxiliary, enantioenriched alpha-SCF3-tetrasubstitued beta-keto esters can be synthesized in good yields with high enantioselectivity.
Review
Chemistry, Organic
Barbara C. Lemos, Eclair Venturini Filho, Rodolfo G. Fiorot, Fabrizio Medici, Sandro J. Greco, Maurizio Benaglia
Summary: This MiniReview compiles the most significant successful examples of highly efficient enantioselective catalytic protocols for the Povarov reaction since 2014, and provides a comprehensive discussion of different catalytic strategies employed in recent years. It also critically discusses the controversial dispute regarding the mechanistic pathways of this well-known reaction.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Review
Chemistry, Organic
Regina Westphal, Eclair Venturini Filho, Fabrizio Medici, Maurizio Benaglia, Sandro J. Greco
Summary: This review summarizes the latest developments in asymmetric domino reactions, with a focus on the preparation of spiro compounds. Discussions on the stereoselectivity of the transformations, reaction mechanisms, rationalization of the stereochemical outcome, and the applications of domino reactions to the synthesis of biologically active molecules and natural products are included.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Multidisciplinary
Fabian Herbrik, Miguel Sanz, Alessandra Puglisi, Sergio Rossi, Maurizio Benaglia
Summary: This study investigated the continuous flow, enantioselective, organophotoredox catalytic asymmetric alkylation of aldehydes using a homemade photoreactor. Significant productivity increase was achieved compared to batch reactions, and the synthesis of an active pharmaceutical ingredient (API) in high enantioselectivity was successfully demonstrated.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Fabian Herbrik, Sergio Rossi, Miguel Sanz, Alessandra Puglisi, Maurizio Benaglia
Summary: A new solid supported Eosin Y has been synthesized and used to build a catalytic continuous flow reactor. The overall productivity of tertiary amines in-flow photooxidations followed by nucleophile addition has increased by one order of magnitude. The resulting Mannich products, obtained using air as the terminal oxidant and in situ generated iminium ions or in a telescoped fashion, have been isolated with high diastereoselectivity and up to 90% enantioselectivity.
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, Organic
Monica Fiorenza Boselli, Niccolo Intini, Alessandra Puglisi, Laura Raimondi, Sergio Rossi, Maurizio Benaglia
Summary: The study investigated the organophotoredox catalytic enantioselective addition of N-acyl radicals to aldehydes, resulting in the formation of enantioenriched N-acyl 1,2 aminoalcohols. Using a low cost and commercially available chiral imidazolidinone as organocatalyst, the product was obtained in up to 52% yield and 85% e.e. under the best conditions in batch reaction. The reaction was further explored in flow, demonstrating higher productivities (up to 60 times higher) and improved space time yields (increased up to 113 times) compared to the batch reaction, while maintaining stereoselectivity.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
F. Medici, F. Montinari, E. Donato, L. Raimondi, M. Benaglia
Summary: A convenient catalytic protocol for the synthesis of electron-poor indoles was developed using Zn(II) salts as catalysts for the cyclisation reaction of electron-deficient 2-(alkynyl)-anilines. This protocol was successfully applied to the synthesis of an API precursor. The use of a readily available, non-noble metal enhanced the value of the protocol.
TETRAHEDRON LETTERS
(2023)
Article
Multidisciplinary Sciences
Maryam Shahzad Shirazi, Mahdi Moridi Farimani, Alireza Foroumadi, Kamal Ghanemi, Maurizio Benaglia, Pooyan Makvandi
Summary: This study successfully synthesized silver oxide quantum dots using ultrasonic irradiation and plant extract, demonstrating their potential applications in the biomedical field with properties such as antioxidant, antibacterial, and antifungal activities. The method presented in this study can be used to develop eco-friendly silver oxide nanoparticles for various biomedical applications.
SCIENTIFIC REPORTS
(2022)
Article
Chemistry, Applied
Milena Krstic, Maurizio Benaglia, Margherita Gazzotti, Eleonora Colombo, Miguel Sanz
Summary: Thiourea-based iminophosphorane (BIMP) organocatalysts, featuring SPhos- or BIDIME phosphine units, have been developed and applied successfully in the asymmetric addition reaction. alpha-Trifluoromethyl beta-nitroamines were obtained with high yields (40-82%) and enantioselectivities (80-95%) on N-Boc-protected trifluoromethyl aryl ketimines. The highest enantioselectivity (up to 95% ee) was achieved by using BIMPs derived from the combination of a chiral 1,2-amino alcohol-derived thiourea-organoazide and electron-rich phosphines via Staudinger reaction.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Review
Chemistry, Physical
Fabrizio Medici, Simonetta Resta, Stefano Andolina, Maurizio Benaglia
Summary: Different approaches have been explored for stereoselective electrochemical synthesis, but the development of general strategies for electrochemical enantiocontrol still faces significant challenges. This review article focuses on the most recent examples of asymmetric electrochemical catalysis, categorized by metal-based catalysis, organocatalysis, and biocatalysis, and discusses the most significant and recent advances in each category.
Article
Chemistry, Multidisciplinary
Eleonora Colombo, Monica Fiorenza Boselli, Laura Raimondi, Alessandra Puglisi, Sergio Rossi
Summary: This study investigated the immobilization of Rose Bengal onto Merrifield resin and its application in the light-driven metal-free thiocyanation of azaheterocycles in continuous reactions. The supported photocatalyst efficiently promoted the reaction under heterogeneous conditions in batch reactions with different azaheterocycles. Its recovery and recyclability were also demonstrated. Under continuous flow conditions, the resin-supported Rose Bengal achieved higher space-time-yields and shorter reaction times compared to batch transformations. Furthermore, the easily modification of the SCN groups was demonstrated by synthesizing trifluoromethyl thioethers and sulfenyl tetrazoles derivatives with high yields.
HELVETICA CHIMICA ACTA
(2023)
Article
Chemistry, Organic
Fabrizio Medici, Alessandra Puglisi, Sergio Rossi, Laura Raimondi, Maurizio Benaglia
Summary: The [2 + 2] photodimerization of cinnamic acid derivatives to afford enantiopure cyclobutanes has been investigated. The use of a chiral auxiliary represents a convenient and straightforward method to exert enantiocontrol on the reaction. By exploiting Evans oxazolidinones, the stereoselective light-driven cyclisation affords a functionalised cyclobutane ring with up to 99% enantiocontrol after removing the chiral auxiliary. In-flow experiments allowed us to improve further the efficiency of the methodology, leading to high conversion and excellent enantioselectivity.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
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)
