Article
Chemistry, Multidisciplinary
Yipin Zhang, Xia Ge, Hongjian Lu, Guigen Li
Summary: Transition-metal-catalyzed sp(2) C-N bond formation is a reliable method for synthesizing aryl amines. This method introduces a cascade approach using organic carboxylic acids and easily prepared azidoformates as carbon and nitrogen sources, achieving high yields and minimal byproducts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Deyun Qian, Srikrishna Bera, Xile Hu
Summary: A nickel-catalyzed hydroalkylation method has been developed to assemble a wide range of chiral alkyl amines with high regio- and enantioselectivity from enecarbamates and alkyl halides. The method is suitable for both nonactivated and activated alkyl halides, producing enantiomerically enriched amines with high functional group tolerance.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Review
Chemistry, Organic
Samata E. Shetgaonkar, Fateh V. Singh
Summary: Hypervalent iodine catalysis is a fast-growing field in hypervalent iodine chemistry. Recent research has focused on the discovery of new chiral hypervalent iodine catalysts and their application in stereoselective reactions. These catalysts have been successful in achieving high enantiomeric excess in various organic transformations.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Rui-Qiang Jiao, Ya-Nan Ding, Ming Li, Wei-Yu Shi, Xi Chen, Zhe Zhang, Wan-Xu Wei, Xue-Song Li, Xiao-Ping Gong, Yu-Yong Luan, Xue-Yuan Liu, Yong-Min Liang
Summary: A glycoarylation reaction of activated olefins under visible-light irradiation has been achieved. Glycosyl radicals are generated by radical transfer strategies involving (TMS)(3)SiOH and glycosyl bromides. Subsequent radical translocation and rapid 1,4-aryl migration lead to the formation of β-sugaramide derivatives, and this reaction is compatible with eight types of sugars. Furthermore, the cascade reaction affords a quaternary carbon center with good functional group adaptability and high regioselectivity under mild conditions.
Article
Chemistry, Organic
Kosho Makino, Kumi Tozawa, Yuki Tanaka, Akiko Inagaki, Hidetsugu Tabata, Tetsuta Oshitari, Hideaki Natsugari, Hideyo Takahashi
Summary: The study revealed that the photoracemization reaction of chiral alkyl aryl sulfoxides is extremely fast and influenced by various substitution patterns. However, chiral sulfoxides with easily oxidizable functional groups are not suitable for this photo-isomerization.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Liang Yan, Manoj K. Jana, Peter C. Sercel, David B. Mitzi, Wei You
Summary: The study presents a new type of 2D hybrid perovskites with a unique combination of chirality and alkyl-aryl functionality, determined by noncovalent intermolecular interactions in their crystal structures. The mixed-cation perovskites exhibit a circular dichroism distinct from purely chiral cation analogues, providing a new avenue for tuning the chiroptical properties of known chiral perovskites. Mixing chiral cations with achiral cations may offer a potential way to tailor the spin-based properties in 2D hybrid perovskites.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Jun Zhu, Yibin Xue, Rui Zhang, Benjamin L. Ratchford, Guangbin Dong
Summary: This article describes a catalytic method for activating unstrained and nonpolar C-C bonds, using removable directing groups to aid in the hydrogenolysis of unstrained C(aryl)-C(alkyl) bonds in 2,2'-methylenediphenols. The method yields high amounts of monophenol products and is tolerant of a wide range of functional groups. Additionally, the reaction is scalable and the catalyst loading can be reduced to as low as 0.5 mol %. The method also proves effective in cleaving C(aryl)-C(alkyl) linkages in both phenolic resins and commercial novolacs resins. Experimental and computational mechanistic studies show that the transformation occurs through a directed C(aryl)-C(alkyl) oxidative addition pathway, with C-H activation being a competitive but reversible off-cycle reaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Zhen Liu, Zi-Yang Qin, Ledong Zhu, Soumitra Athavale, Arkajyoti Sengupta, Zhi-Jun Jia, Marc Garcia-Borras, K. N. Houk, Frances H. Arnold
Summary: Propargyl amines are versatile synthetic intermediates with numerous applications in the pharmaceutical industry. An enzymatic platform for enantioselective propargylic amination of alkynes using a hydroxylamine derivative as the nitrene precursor was developed in this study. The biocatalytic process showed high efficiency and selectivity, making it a promising approach for industrial applications.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Daniel L. Jensen, Helle H. Trinderup, Frederik Skovbo, Henrik H. Jensen
Summary: A new and environmentally friendly protocol for the conversion of sugar per-acetates into thioglycosides is presented. The procedure involves heating in the presence of InCl3 and various aryl thiols. The established optimum reaction conditions provide the desired thioglycoside products in an easy and highly diastereoselective manner, even on a multigram scale.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Shuai Liu, Yangen Huang, Juan Wang, Feng-Ling Qing, Xiu-Hua Xu
Summary: This study reports a method for the design and synthesis of novel N-Cbz- and N-Boc-N-trifluoromethyl hydroxylamine reagents using silver-mediated oxidative trifluoromethylation. These reagents have been successfully applied to incorporate a NCF3 moiety into commonly used unsaturated substrates, enabling efficient and regioselective C-H trifluoromethylamination. Additionally, a variety of substrates can undergo tandem trifluoromethylamination/functionalization to deliver structurally diverse N-trifluoromethyl aliphatic and heteroaromatic amines.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Multidisciplinary Sciences
Lumin Zhang, Bethany M. DeMuynck, Alyson N. Paneque, Joy E. Rutherford, David A. Nagib
Summary: Carbenes, highly reactive intermediates, are successfully generated from common aldehydes via stable alpha-acyloxy halide intermediates, enabling diverse and valuable chemistry reactions. This strategy utilizes zinc carbenoids and earth-abundant metal salts as catalysts to achieve safe and selective carbene additions to sigma and pi bonds.
Article
Chemistry, Organic
Kotoko Makino, Yuhei Kumagai, Tatsuhiko Yoshino, Masahiro Kojima, Shigeki Matsunaga
Summary: A chiral paddle-wheel dinuclear ruthenium catalyst demonstrates superior substrate scope compared to analogous chiral paddle-wheel rhodium catalysts in catalytic asymmetric nitrene-transfer reactions with enol silyl ethers. Up to 97% ee of alpha-amino ketones can be obtained from aliphatic substrates using the ruthenium catalyst, while similar rhodium catalysts yield only moderate enantioselectivity.
Article
Chemistry, Multidisciplinary
Nasim Khan, Katsunori Itaya, Thomas Wirth
Summary: New iodotriptycenes, including chiral derivatives, have been synthesized and their catalytic potential in oxidative transformations has been investigated. The enantioselectivities of the products using chiral iodotriptycene catalysts are low, likely due to the large distances between the coordinating groups and the iodine moieties in these compounds.
Article
Chemistry, Multidisciplinary
Meng-Meng Liu, Yankun Xu, Chuan He
Summary: In this study, a highly enantioselective synthesis of silicon-stereogenic silazanes was achieved through catalytic dehydrogenative coupling of dihydrosilanes with anilines. The reaction synthesized various chiral silazanes and bis-silazanes with excellent yields and stereoselectivities (up to 99% ee). Further applications included the construction of polycarbosilazanes with configurational main chain silicon-stereogenic chirality, and the transformation of the enantioenriched silazanes into various chiral silane compounds, demonstrating their potential utilities as synthons for novel silicon-containing functional molecules.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Anton A. Gladkov, Vitalij V. Levin, Alexander D. Dilman
Summary: The reaction between organozinc reagents and unactivated imines is enhanced under blue light irradiation in the presence of a photocatalyst. The coordination between Lewis acidic zinc iodide and the imine plays a crucial role in improving reaction efficiency. This method can be carried out using alkyl iodides under Barbier conditions.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
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
Biochemistry & Molecular Biology
Milena Krstic, Sergio Rossi, Miguel Sanz, Alessandra Puglisi
Summary: The enantioselective synthesis of optically active alpha-amino acid derivatives using achiral Schiff base esters has been well-developed in batch, and recent studies have explored its application in continuous flow systems. Two different methodologies were investigated, with liquid-liquid phase transfer catalysis showing slightly better productivity and solid-liquid phase transfer catalysis proving more advantageous in terms of productivity and space-time yield. The continuous flow system also allowed for the isolation of the benzylated product without any additional work up, simplifying the process. Both methods showed high enantioselectivity, with up to 93% ee achieved in the continuous flow phase transfer benzylation promoted by Maruoka catalyst.
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)
Review
Chemistry, Multidisciplinary
Dan He, Yawen Li, Fuwen Zhao, Yuze Lin
Summary: High trap density in organic solar cells leads to localized charge carriers and reduced carrier lifetime, limiting device efficiency. This feature article summarizes the recent advances of trap suppression by material design and device engineering.
CHEMICAL COMMUNICATIONS
(2024)
Review
Chemistry, Multidisciplinary
Olivier Monfort, Arshitha Madhusudhan, Martin Motola
Summary: This article presents the advantages of coupling photocatalysis and Fenton-based processes for environmental remediation and discusses their synergy. It critically examines the simultaneous triggering of these two processes and provides insights into research approaches. The study aims to enhance understanding of this complex process and highlight the potential integration of new catalysts in current wastewater treatment technology.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Manideepa Dhar, Chittaranjan Mishra, Avijit Das, Uttam Manna
Summary: An approach of 'polymerization of monomers in its aggregated form' has been introduced to tailor the water wettability of fibrous and porous substrates, achieving hydrophobicity to superhydrophobicity transition, as well as patterned wettability. This facile chemical method provides a durable coating with adjustable and patterned wettability for various potential applications.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Saswat Ranjan Bhoi, Chhanda Debnath, Shikha Gandhi
Summary: In this article, a novel catalytic reaction using Pd(0) and Bronsted acid is reported for the synthesis of biologically important imidazolidinone-fused N-heterocycles through redox-neutral intramolecular N-allylation of indoles and pyrroles with alkynes. This atom-economical method is applicable to a wide range of substrates and eliminates the need for leaving groups or oxidizing agents commonly used in traditional allylation reactions.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Longkun Chen, Mingshuai Zhang, Meichen Liu, Zhuoyuan Liu, Yuetong Qiu, Zhilai Zhang, Fuchao Yu, Jiuzhong Huang
Summary: In this study, an efficient Rh(III)-catalyzed selective mono- and dual-C-H bond functionalization/cyclization with iodonium ylide as the sole coupling partner was demonstrated. Fused benzodiazepine skeletons were obtained in excellent yields, providing an improved approach to dual C-H unsymmetrical functionalization.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Alice Kennett, Sven Epple, Gabriella van der Valk, Irene Georgiou, Evelyne Gout, Romain R. Vives, Angela J. Russell
Summary: This study presents the design and synthesis of sulfated disaccharide inhibitors based on IdoA(2S)-GlcNS(6S), which showed potent inhibition of Sulf-2. The results suggest that IdoA(2S)-GlcNS(6S) is the shortest fragment size required for effective inhibition of Sulfs, and a trisulfated disaccharide is identified as the minimal fragment size of heparan sulfate for effective endosulfatase inhibition.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Mauro Garbini, Andrea Brunetti, Riccardo Pedrazzani, Magda Monari, Massimo Marcaccio, Giulio Bertuzzi, Marco Bandini
Summary: The self-adaptability of galvanostatic electrolysis was found to be helpful in a multistage chemo- and diastereoselective electrochemically promoted cyclodimerization of chalcones. Through a series of reductive events, densely functionalized cyclopentanes with five contiguous stereocenters were obtained (25 examples, yields up to 95%, dr values up to >20:1). Further experimental and electrochemical investigations indicated the crucial role of dynamic kinetic resolution of the aldol intermediate in the reaction mechanism.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Dhananjay S. Nipate, Neha Meena, Prakash N. Swami, Krishnan Rangan, Anil Kumar
Summary: In this study, the synthesis of functionalized benzo[a]phenazines and indazolo[2,3-a]quinolines was achieved through Rh(III)-catalyzed oxidative annulation of 2-arylquinoxalines and 2-aryl-2H-indazoles with allyl alcohols. The method showed a wide substrate scope, excellent functional group tolerance, good to high yields of annulated products, and the capability for scaled-up synthesis. A tentative mechanism of the annulation reaction was proposed based on a preliminary mechanistic investigation.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Ruonan Zhang, Abudukadi Tudi, Xia Yang, Xuping Wang, Zhihua Yang, Shujuan Han, Shilie Pan
Summary: A new lead tellurium borate material with a unique fundamental building block [B4O10] was synthesized and found to exhibit high birefringence. The structure-property relationship was discussed using first-principles calculations.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Amresh Kumar Singh, Baishali Thakurta, Anupam Giri, Monalisa Pal
Summary: This study introduces three key concepts for the quick synthesis of large-scale high-quality 2D materials films and their utilization in device fabrication.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Reina Hagiwara, Shun Nishimura, Kosuke Okeyoshi
Summary: A copolymer-conjugated nanocatalytic system has been developed to improve electron transfer and enhance photoinduced H2 generation.
CHEMICAL COMMUNICATIONS
(2024)
