Article
Chemistry, Organic
Xia Wang, Peng Yang, Bo Hu, Qian Zhang, Dong Li
Summary: A novel transformation of primary amides to secondary amides was developed using hypervalent iodine reagents, promoting a Hofmann-type rearrangement to generate an isocyanate intermediate which was then trapped by a carboxylic acid from the same reagent to provide the corresponding secondary amides. This method not only offers an easy and efficient route for synthesizing secondary amides from primary amides, but also reveals novel reactivities of hypervalent iodine reagents.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Chenyang Wang, Peng Shi, Carsten Bolm
Summary: In this study, dichloro- and dibromomethane were utilized as halogen sources to convert NH-sulfoximines to N-halo derivatives, using an in situ formed sulfoximidoyl-containing hypervalent iodine reagent under visible light. The reactions were carried out in air without the need for catalysts or additives, and the products were obtained in good to excellent yields.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Jorna Kalim, Thibaut Duhail, Ewa Pietrasiak, Elsa Anselmi, Emmanuel Magnier, Antonio Togni
Summary: A study has discovered a method for direct trifluoromethylation of various aliphatic alcohols using a hypervalent iodosulfoximine reagent, resulting in the efficient synthesis of corresponding ethers.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Jiang Nan, Xin Ren, Qiang Yan, Shilei Liu, Jing Wang, Yangmin Ma, Michal Szostak
Summary: A novel hypervalent iodine-induced twofold oxidative coupling of amines with amides and thioamides has been established, which chemoselectively assembles oxazoles and thiazoles. The mechanism involves the generation of ureas and thioureas as intermediates. These findings open up new avenues for exploring oxidative bond chemistry of amides and thioamides.
Article
Chemistry, Multidisciplinary
Xuan Cheng, Quan Yin, Yu-Xuan Jiang, Ling-Feng Jiang, Si-Yuan Li, Yi-Fei Cheng, Xin-Chang Sun, Lujun Peng, Cheng Zhong, Qing-Hai Deng
Summary: In this study, bench-stable and highly reactive noncyclic hypervalent iodine nitrooxylating reagents were developed for efficient access to organic nitrates. These reagents showed excellent performance in regioselective nitrooxylation of cyclopropyl silyl ethers and catalyst-free nitrooxylation of enolizable C-H bonds. The protocol provides a practical and direct approach to various organic nitrates.
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
Xiao-Guang Yang, Feng-Huan Du, Jun-Jie Li, Chi Zhang
Summary: A practical method for dehydroxyazidation of alcohols using PPh3 and hypervalent azido-iodine(III) reagents is reported. The method allows for the late-stage azidation of structurally complex alcohols and the synthesis of the antiepileptic drug rufinamide.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Yu Zheng, Tianting Ma, Bingcong Liu, Shenlin Huang
Summary: A direct and efficient method for the synthesis of 3-chloro-2-formylindoles using SO2ClF is reported. This tandem system involves electrophilic chlorination, deprotonation, nucleophilic addition, and oxidation. Under mild conditions, various 2-methylindoles can be successfully transformed into 2,3-difunctionalized indoles in good yields.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Review
Chemistry, Organic
Yaxin O. Yang, Xi Wang, Jiaxi Xiao, Yadong Li, Fengxia Sun, Yunfei Du
Summary: In the past decades, hypervalent iodine chemistry has flourished, especially in bond-forming reactions involving the formation of C-N bond, providing a wide range of applications for constructing various heterocyclic skeletons and useful building blocks under metal-free conditions.
CURRENT ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Jason D. Bennetts, Lachlan Barwise, Lachlan Sharp-Bucknall, Keith F. White, Conor F. Hogan, Jason L. Dutton
Summary: The structure of Stang's reagent [PhI(CN)][OTf] is confirmed by X-ray crystallography as an ion-pair in organic solution. It is a strong Lewis acid and reacts with pyridine ligands, resulting in the formation of [Pyr-CN][OTf] salts and a new derivative of CDAP reagent commonly used for polysaccharide activation.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Applied
Qin He, Zehui Cao, Yangyang Zhang, Gong Chen, Yaxin Wang
Summary: A novel radical reaction system mediated by azidobenziodoxole (BIN3) was developed for selective chlorination and bromination of tertiary and secondary C(sp(3)) H bonds of alkyl substrates using haloform as the halogen donor. The reactions of various substrates with BIN3 under visible light irradiation yielded C-H chlorinated or brominated products without the need for any photo or metal catalysts. The mechanism involves haloform serving as the halogen atom donor and HN3 generated in situ from the reaction of BIN3 and water as the hydrogen atom donor, which propagate a radical chain reaction by abstracting a hydrogen atom from the alkane substrate.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Julien Borrel, Jerome Waser
Summary: In this study, a simplified synthesis method for generating Ethynylbenziodoxolones (EBXs) in one pot and directly applying them to substrate functionalization was reported. By bypassing the mandatory isolation and purification steps, this approach led to a more efficient synthesis and successful application in various transformations to obtain a diverse range of alkynylated products.
Review
Chemistry, Organic
Chunngai Hui, Andrey P. Antonchick
Summary: This study introduces a new reactive electrophilic aminating reagent, iodonitrene, which can transfer NH-group directly to nucleophilic atoms and has led to the development of new reactions. The application of iodonitrene has promising prospects, although there are current limitations.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Mattis Damrath, Lucien D. Caspers, Daniel Duvinage, Boris J. Nachtsheim
Summary: Two simple methods for synthesizing O- and N-bridged diaryliodonium triflates are described. Different derivatizations were applied to demonstrate their usefulness as building blocks and to gain a deeper understanding of their general reactivity.
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, 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)