Article
Chemistry, Multidisciplinary
Lijun Shi, Mingshan Wen, Fuwei Li
Summary: The study reports a selective method for the synthesis of fused N-heterocycles through palladium-catalyzed tandem reactions, which successfully addresses the selectivity issue in the presence of incompatible step reactions and effectively prevents side reactions.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Organic
Jingjing He, Chuan Liu, Yupian Deng, Qianding Zeng, Yi Zhang, Ying Liu, Pai Zheng, Song Cao
Summary: A mild and efficient DBN-mediated addition reaction was developed for the synthesis of various β-trifluoromethyl nitrogen-containing heterocycles and β-trifluoromethyl amines using α-(trifluoromethyl)styrenes and diazoles, triazoles, tetrazoles, and primary, secondary, and secondary cyclic amines.
Review
Chemistry, Applied
Seoung-Mi Choi, Ju Hyun Kim
Summary: This review summarizes the progress made in the synthesis of 2H-pyrroles since 2000, including methods such as dearomatization of 1H-pyrrole, oxidation of pyrrolines or pyrrolidines, ring construction via catalytic cycloaddition, and rearrangement of 3H-pyrroles.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Suman Pradhan, Sampurna Das, Gautam Kumar, Indranil Chatterjee
Summary: The unique property of hexafluoroisopropanol (HFIP) enables the regioselective hydroamination of 1,3-dienes with nitrogen heterocycles in a Markovnikov manner in the presence of catalytic Bronsted acid. This transition-metal-free intermolecular hydroamination protocol is achieved under mild reaction conditions. The aggregation by HFIP and Brensted acid helps to activate the terminal double bond regioselectively, leading to protonation of the diene and subsequent C-N bond formation with heterocyclic amines.
Article
Chemistry, Organic
Linpeng Liu, Yanyu Jian, Weigao Hu, Shaohu Zhao, Zhang-Jie Shi, Nicklas Selander, Taigang Zhou
Summary: A method for radical cyclization and ring-opening of oxime esters with diselenides has been developed. Both Ni(0) and Fe(ii) catalysts can be used for the selenylation of olefin-containing and cyclic oxime ester derivatives. Using this method, a variety of functionalized pyrrolines and alkyl nitriles can be synthesized in good yields. Additionally, a mechanism involving iminyl radical and carbon-centered radical intermediates has been proposed.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Jin-Feng Lv, Yu-Fang Tan, Ya-Nan Zhao, Dan Yang, Yan-Hong He, Zhi Guan
Summary: The paper describes an electrochemical method for the synthesis of N-vinyl benzotriazoles by coupling olefins with benzotriazoles to form C(sp(2))-N bonds. It is a highly atom-economic and clean reaction, with nBu4NI serving as both an electrolyte and an iodine mediator, and hydrogen as the only byproduct.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Qing-Qing Kang, Yi Liu, Shi-Ping Wu, Guo-Ping Ge, Hongxing Zheng, Jun-Qi Zhang, Wen-Ting Wei
Summary: An efficient radical cyclization of 1,6-dienes with alkyl nitriles was achieved through alpha-C(sp(3))-H functionalization under the Sc(OTf)(3) and Ag2CO3 system, relying on the substitution effect at the alpha-position of acrylamide moiety and nitriles. The reaction pathway involves hydrogen abstraction, direct cyclization with the aryl ring, or further cyclization with the C = N bond and hydrolysis.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Review
Chemistry, Organic
Christian Dank, Laura Ielo
Summary: This review article discusses the recent progress in the biological and chemical evolution of aziridine derivatives, with a focus on the synthesis of aziridines and their transformation reactions. These compounds have shown great potential from both synthetic and pharmacological perspectives and have attracted significant attention due to their promising biological activities.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Nuria Vazquez-Galinanes, Isabel Velo-Heleno, Martin Fananas-Mastral
Summary: A method for the use of vinyl epoxides in catalytic allylboration of alkynes is described, which allows for the synthesis of bifunctional skipped dienes bearing both an allylic alcohol and an alkenylboronate from simple starting materials with high regio- and stereoselectivity. These products show versatile reactivity and can be converted into cyclic boron compounds and polyenes.
Article
Chemistry, Multidisciplinary
Enrico Bergamaschi, Danijela Lunic, Liam A. McLean, Melissa Hohenadel, Yi-Kai Chen, Christopher J. Teskey
Summary: This study demonstrates, for the first time, the ability to use light to distinguish between ketones and carboxylic acids in more complex molecules. By utilizing different activation modes, a single catalytic system can be used for hydroboration, with chemoselectivity dictated solely by the presence or absence of visible light.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Johanna Templ, Edma Gjata, Filippa Getzner, Michael Schnuerch
Summary: In this study, we used phenyl trimethylammonium iodide as a reagent to achieve highly selective methylation of amides and indoles. The method is easy to use, provides high yields, has good functional group tolerance, and is particularly suitable for late-stage methylation of bioactive compounds.
Article
Chemistry, Organic
Na Meng, Wensheng Yu, Takao Suzuki, Maofen Chen, Zhiqi Qi, Bin Hu, Jianming Bao, John S. Debenham, Robert Mazzola, Joseph L. Duffy
Summary: The deoxygenation of substituted methanol derivatives using PPh3/I-2/imidazole was successful for secondary or tertiary alcohols with one or two heteroaryl groups, and it tolerated acid-sensitive heterocycles. While it worked for methanol derivatives with 2-pyridyl, 4-pyridyl, or other heterocyclic groups, those with 3-pyridyl or heterocyclic groups that do not allow resonance of the negative charge to a nitrogen atom did not undergo deoxygenation under this condition.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Fabio Julia, Jiyao Yan, Fritz Paulus, Tobias Ritter
Summary: A vinyl thianthrenium salt has been introduced as an effective vinylating reagent, which can be readily prepared from ethylene gas and is broadly useful in various annulation chemistry reactions. Its unique structural features enable a distinct synthesis and reactivity profile, unprecedented for other vinyl sulfonium derivatives.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Applied
Raffaella Mancuso, Patrizio Russo, Melania Lettieri, Domenico Santandrea, Corrado Cuocci, Bartolo Gabriele
Summary: Polycyclic heterocyclic derivatives can be synthesized in one step by a carbonylative double cyclization approach, with yields ranging from 45% to 86%, showing promising potential for various applications.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Review
Chemistry, Organic
Rizk E. Khidre, Ibrahim M. A. Radini, Tahah A. Ameen, Ahmed A. M. Abdelgawad
Summary: This review discusses the synthetic methods and pharmacological properties of [1,2,3]triazoloquinoline derivatives, including the ten isomers based on the junction between triazole and quinoline. The synthetic methods are categorized into groups based on the type of isomers, and the pharmacological activity of [1,2,3]triazoloquinoline is also addressed in the review.
CURRENT ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Raphael Simonet-Davin, Jerome Waser
Summary: In this short review, applications of hypervalent iodine reagents for the azidation of organic compounds were described, with a focus on stable cyclic reagents. Important advances in the azidation of C-H bonds, alkenes, and other transformations were highlighted through selected key reports.
SYNTHESIS-STUTTGART
(2023)
Review
Chemistry, Multidisciplinary
Eliott Le Du, Jerome Waser
Summary: Although small, alkynes are highly versatile building blocks in organic chemistry, with applications ranging from biochemistry to material sciences. Traditional alkynylation reactions rely on the use of acetylenes as nucleophiles. However, the discovery and development of ethynyl hypervalent iodine reagents have greatly expanded the transfer of alkynes as electrophilic synthons. This feature article presents the progress in the field since 2018, including synthesis of alkynyl hypervalent iodine reagents, their use in base-mediated and transition-metal catalyzed alkynylations, and progress in radical-based alkynylations and atom-economical transformations.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Stephanie G. E. Amos, Franck Le Vaillant, Jerome Waser
Summary: Alkynes and nitriles are important building blocks in organic synthesis, chemical biology, and materials science. This study investigates the conversion of alcohols into alkynes and nitriles using cesium oxalates and Ethynyl BenziodoXolones (EBXs), and explores the effects of backbone modification of EBXs on the deoxyalkynylation of cesium oxalates. Preliminary data on the development of new deoxycyanation and dethioalkynylation processes are also presented, along with the serendipitous discovery of C-H alkynylation of 1,2-dichloroethane.
HELVETICA CHIMICA ACTA
(2023)
Article
Chemistry, Multidisciplinary
Emma G. L. Robert, Vincent Pirenne, Matthew D. Wodrich, Jerome Waser
Summary: A convenient method for the one-step synthesis of beta-aminocyclobutane monoesters using commercially available reagents is reported. The obtained strained rings undergo dearomative annulation with indole partners using silylium catalysis, providing tricyclic indolines with four new stereocenters. The reaction can proceed both intra- and intermolecularly and the outcome can be selectively controlled based on reaction temperature, resulting in the formation of either akuamma or malagasy alkaloid-like tetracyclic structures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Xing-Yu Liu, Xinjian Ji, Christian Heinis, Jerome Waser
Summary: We present a new method for modifying peptides using highly reactive hypervalent iodine reagents called ethynylbenziodoxolones (EBXs). These peptide-EBXs can be easily synthesized through solution- and solid-phase peptide synthesis (SPPS). They can be used to couple peptides to other peptides or proteins via reaction with Cys, resulting in thioalkynes in organic solvents or hypervalent iodine adducts in water buffer. Additionally, a photocatalytic decarboxylative coupling to the C-terminus of peptides was developed, leading to macrocyclic peptides with unprecedented crosslinking.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Nieves P. P. Ramirez, Jerome Waser
Summary: An asymmetric 3-component reaction catalyzed by a Cu-I-BOX catalyst was developed for the synthesis of chiral trifluoromethylated propargyl ethers and anilines. The reaction showed high enantioselectivity and yield with various nucleophiles and different electrophiles. The method also exhibited good diastereoselectivity with chiral substrates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Eliott Le Du, Nieves P. Ramirez, Stefano Nicolai, Rosario Scopelliti, Farzaneh Fadaei-Tirani, Matthew D. Wodrich, Durga Prasad Hari, Jerome Waser
Summary: First synthesized in 1991, EthynylBenziodoXolones (EBXs) are now among the most versatile electrophilic alkynylation reagents. Due to their cyclic structure, these reagents exhibit enhanced stability compared to previously used alkynyl iodonium salts. The collected structural data of EBXs and their analogues, along with the calculated molecular electrostatic potentials (MEP), is expected to be highly useful for further developments in the field, considering the tight relationship between structure and reactivity in hypervalent iodine reagents.
HELVETICA CHIMICA ACTA
(2023)
Article
Chemistry, Multidisciplinary
Tobias Michael Milzarek, Jerome Waser
Summary: The first trifluoromethylation of vinylbenziodoxolones (VBX) using bench-stable, high-valent copper(III) species is reported. The reaction can be initiated under thermal conditions and/or irradiation (365 nm) and leads to stereoselective formation of trifluoromethylated alkenes. Various VBX reagents derived from tyrosine, cysteine, small peptides, thiols, and amides can be used as precursors. The obtained alkenes can be further functionalized through reduction or epoxidation of the trifluoromethylated double bond. The method is suitable for large-scale batch/flow synthesis and can be conducted under visible light irradiation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Ilias Koutsopetras, Abhaya Kumar Mishra, Rania Benazza, Oscar Hernandez-Alba, Sarah Cianferani, Guilhem Chaubet, Stefano Nicolai, Jerome Waser
Summary: Peptide and protein bioconjugation is increasingly important in the pharmaceutical industry. This study introduces the crosslinking ethynylbenziodazolone (EBZ) reagent JW-AM-005 for selective conjugation of peptides and proteins using cysteine residues. The reagent allows for the formation of peptide dimers or stapled peptides under mild and tuneable conditions. Additionally, it demonstrates high regioselectivity in the rebridging of antibody fragments, surpassing commonly used reagents for this transformation.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Oleksandr S. Liashuk, Oleksandr O. Grygorenko, Yulian M. Volovenko, Jerome Waser
Summary: A photochemical [2+2] cycloaddition reaction between alkynyl boronates and maleimides is reported. The reaction exhibited wide compatibility with different functional groups and provided 35-70% yield of maleimide-derived cyclobutenyl boronates. The prepared building blocks showed synthetic utility in various transformations, including cross-coupling, reduction, oxidation, and cycloaddition reactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Vladyslav Smyrnov, Jerome Waser
Summary: An electrophile-induced semipinacol rearrangement of cyclopropenylcarbinols is described, enabling the synthesis of polyfunctionalized cyclopropanes under mild metal-free conditions. The reaction demonstrates broad scope, accommodating various electrophiles, migrating groups, and substitution patterns on the cyclopropene. It is particularly useful for the synthesis of small ring-containing spirocycles, which are important building blocks in medicinal chemistry.
Article
Chemistry, Organic
Pierre Palamini, Julien Borrel, Mael Djaid, Morgane Delattre, Jerome Waser
Summary: We report the synthesis of ketene dithioarylacetals in 40-97% yield using thiophenols and acyl-EBXs generated in situ from a common hypervalent iodine precursor and alkynyl trifluoroborate salts. The products could be further modified to afford functionalized ketene dithioacetals and various S-substituted heterocycles.
Article
Chemistry, Multidisciplinary
Julien Borrel, Jerome Waser
Summary: We present a method for azidoalkynylation of alkenes, which provides a straightforward route to homopropargylic azides by using hypervalent iodine reagents and alkynyltrifluoroborate salts. The development of a photocatalytic redox-neutral radical polar crossover process was crucial for this transformation. A range of homopropargylic azides with electron-rich and -poor aryls, heterocycles, or ether substituents could be obtained in yields of 34-84%. These products serve as valuable building blocks that can be easily converted into pyrroles or bioactive amines.
Article
Chemistry, Multidisciplinary
Mikus Purins, Lucas Eichenberger, Jerome Waser
Summary: We present a mild approach for the synthesis of propargyl silanes from terminal alkynes. A bromonaphthyl-substituted silane was used as a silylmethyl electrophile surrogate, which underwent an aryl-to-alkyl Pd-migration followed by a Sonogashira reaction. A total of 27 propargyl silanes were obtained with yields up to 88%. The resulting products serve as versatile building blocks for addition reactions with electrophiles, triple bond hydrogenation, or silyl group cleavage with acid or fluoride sources.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Tobias M. Milzarek, Nieves P. Ramirez, Xing-Yu Liu, Jerome Waser
Summary: Bis(trifluoromethylated)benziodoxoles are widely used cyclic hypervalent iodine reagents with stability and unique chemical properties. However, current methods for accessing them are tedious. This study reports a direct one-pot synthesis of bis(trifluoromethylated) Bx reagents, enabling the synthesis of functionalized reagents.
CHEMICAL COMMUNICATIONS
(2023)