Article
Chemistry, Organic
Du Chen, Liangxuan Xu, Bowen Ren, Zian Wang, Chao Liu
Summary: An effective method for synthesizing amides and esters at ambient temperature within 5 minutes has been developed, using a stable and easily accessible triflylpyridinium reagent. Remarkably, this method not only has a wide range of substrate compatibility, but also enables scalable synthesis of peptides and esters through continuous flow process. Moreover, it demonstrates excellent chirality retention during carboxylic acid activation.
Article
Chemistry, Organic
Nathaniel R. Luis, Kasey K. Chung, Matthew R. Hickey, Ziqing Lin, Gregory L. Beutner, David A. Vosburg
Summary: This Communication presents the investigation of using the combination of N,N,N',N'-tetramethylchloroformamidinium hexafluorophosphate (TCFH) and N-methylimidazole (NMI) for the synthesis of esters and thioesters. The study reveals the challenges in reactions involving less nucleophilic alcohols and more reactive thiols with the N-acyl imidazolium intermediate. However, general enabling conditions have been identified to achieve high yields and selectivity for a range of alcohols and thiols.
Review
Chemistry, Applied
Paola Acosta-Guzman, Andrea Ojeda-Porras, Diego Gamba-Sanchez
Summary: The construction of amide bonds is of great interest due to their prevalence in bioactive molecules. This review presents the most viable strategies for constructing amide bonds, with a focus on recent developments in the field.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
You-Wei Wu, Mu-Xiang Chen, Yan Li, Lu-Min Hu, Lili Zhao, Zhenhua Jia, Xuefei Zhao, Xu-Hong Hu
Summary: A distinct protocol for secondary amide formation through a catalyst- and additive-free cross-coupling of isocyanates with triarylboranes has been described, avoiding the use of moisture-sensitive organometallics, transition metals, or any additives, and accessing valuable amides through aryl migration.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Alexander O. Terent'ev, Igor B. Krylov, Ilya V. Kuzmin, Oleg O. Segida, Andrey V. Lastovko, Mikhail I. Shevchenko, Gennady I. Nikishin, Alexander O. Terent'ev
Summary: The field of free-radical reagents in organic chemistry has focused on aminoxyl radicals for a long time. Diacetyliminoxyl, a readily synthetically available oxime radical, differs from aminoxyl radicals in structure and reactivity, demonstrating exceptional stability and reactivity when used as a radical reagent in organic synthesis. It has shown selectivity in abstracting hydrogen from activated substrates or functional groups and has proven to be effective in intercepting stabilized and sterically hindered C-radicals that cannot be trapped by typical radical scavengers like TEMPO.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Tao Liu, Xue Zhang, Zejun Peng, Junfeng Zhao
Summary: The novel ynamide coupling reagent allows removal of by-products by water, facilitating direct coupling reactions between carboxylic acids and amines, alcohols, or thiols to produce amides, peptides, esters, and thioesters. The reactions do not exhibit detectable racemization, and a simple acidic aqueous work-up enables the attainment of pure products with good yields. The water-removable ynamide coupling reagent has been successfully demonstrated in the synthesis of carfilzomib without the need for column chromatography purification.
Article
Chemistry, Organic
Thomas Lainer, Frank Czerny, Michael Haas
Summary: This study describes a solvent-free procedure for the formation of amides in the presence of air and moisture. By using specific coupling agents, carboxylic acids and amines can react to form amides with good to excellent yields. Neopentasilane 3 shows superior performance in terms of group tolerance and yield compared to the currently used monosilanes as coupling agents.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Applied
Sofia Strekalova, Alexander Kononov, Vladimir Morozov, Olga Babaeva, Elena Gavrilova, Yulia Budnikova
Summary: This study describes the electrochemical amidation of C(sp2)-H and C(sp3)-H bonds of a wide range of arenes using nitriles as amide sources, achieved under mild conditions without the need for metal catalysts or external oxidizing agents. The method offers moderate to high yields, can be applied to arenes with diverse functional groups, and is suitable for gram scale synthesis. The key role of the hydroxyl radical as an inductor generated during the oxidation of water has been established through EPR experiments.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Tao Liu, Silin Xu, Junfeng Zhao
Summary: Coupling reagents can promote the direct condensation of carboxylic acids with amines or alcohols to form amide or ester bonds, widely used in drug, material, and cosmetic production. However, issues such as impurities and racemization caused by over activation of traditional coupling reagents, as well as large chemical waste from solid phase peptide synthesis, call for new reagents and mechanisms to address them.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Biochemistry & Molecular Biology
Nicholas Favalli, Gabriele Bassi, Davide Bianchi, Joerg Scheuermann, Dario Neri
Summary: Progress in DNA-encoded chemical library synthesis relies on DNA-compatible reactions, and in this study, optimized Suzuki and Sonogashira reactions showed good conversion rates for a variety of building blocks. Additionally, efficient experimental conditions for on-DNA synthesis of amide bonds were described, highlighting the importance of excellent DNA compatibility in chemical library synthesis.
BIOORGANIC & MEDICINAL CHEMISTRY
(2021)
Article
Multidisciplinary Sciences
Wei Liu, Marissa N. Lavagnino, Colin A. Gould, Jesus Alcazar, David W. C. MacMillan
Summary: The S(H)2 mechanism has been utilized in the synthetic formation of organic molecules to create quaternary sp(3)-carbon centers. The mechanism involves distinguishing between primary and tertiary carbons to form S(H)2 bonds and generating radical classes simultaneously from abundant functional groups using photocatalysis.
Article
Chemistry, Multidisciplinary
Robin Dinter, Suzanne Willems, Mahdi Hachem, Yana Streltsova, Andreas Brunschweiger, Norbert Kockmann
Summary: Synthesis platforms play a crucial role in DNA-encoded library (DEL) technologies for the development of chemistry, validation of building blocks, and high-throughput library synthesis. In this study, a liquid-liquid two-phase flow reactor was designed to enable parallel reactions on DNA-coupled substrates. A coiled flow inverter (CFI) tubular reactor with a 3D-printed internal structure was used for improved mixing and compact setup. By generating slugs containing different carboxylic acids, individual reaction compartments representing single batch experiments were successfully created, allowing for parallelized reactions.
REACTION CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Organic
Bingyang Miao, Meng Xue, Shuaiyu Ji, Zonghua Wang, Yuexia Zhang
Summary: Here, a new method of methylenation of alcohols using N-methyl amide as a sustainable methylene reagent is reported; the N-methyl group delivers the methylene group. This new reagent is easily prepared and stable to both air and moisture. Furthermore, the final byproduct of this methylene reagent can be recycled in excellent yields and then reused in methylenation reactions upon treating with CH3I.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Nina X. Gu, Paul H. Oyala, Jonas C. Peters
Summary: The formation of Ni-III-NH2 species that undergo bimolecular coupling to generate a Ni-2(II)(N2H4) complex is discussed in this study. Further oxidation to a structurally unusual Ni-2(N2H2) species releases N-2, establishing a synthetic cycle for Ni-mediated AO using Earth-abundant, late first-row metals.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Engineering, Chemical
Gehui Pang, Shintaro Morisada, Hidetaka Kawakita, Takeshi Hanamoto, Tatsuya Umecky, Keisuke Ohto, Xi-Ming Song
Summary: In this study, two secondary amide compounds with and without fluorine atoms were synthesized and found to exhibit different extraction selectivity for Ga(III) in competitive solutions. Through spectroscopic analysis and determination of stoichiometries, it was revealed that the protonation state of the extraction reagents and the concentration of HCl play crucial roles in the extraction mechanism and efficiency of Ga(III) extraction.
SEPARATION AND PURIFICATION TECHNOLOGY
(2022)
Article
Chemistry, Multidisciplinary
Morgane Sayes, Guillaume Benoit, Andre B. Charette
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2018)
Article
Chemistry, Multidisciplinary
Maude Aelterman, Morgane Sayes, Philippe Jubault, Thomas Poisson
Summary: In this study, electrochemical hydroboration of alkynes using B(2)Pin(2) as the boron source was reported. This method showed good applicability across a wide range of alkynes with high yields, without the need for a metal catalyst or a hydride source. The transformation relied on the potential electrochemical oxidation of an in situ formed borate to introduce a putative boryl radical that reacted with the alkyne.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Lea Thai-Savard, Morgane Sayes, Josiane Perreault-Dufour, Gang Hong, Lucille A. Wells, Marisa C. Kozlowski, Andre B. Charette
Summary: The borosilylcyclopropanation of styrene derivatives using a (diiodo(trimethylsilyl)methyl)boronic ester carbene precursor is reported, with the key reagent synthesized in a 4-step sequence using inexpensive and commercially available starting materials. This method enables the preparation of novel 1,1,2-tri- and 1,1,2,2-tetrasubstituted borosilylcyclopropanes with excellent yields and diastereoselectivity. The organocatalyzed reaction by eosin Y in the presence of visible light follows a postulated mechanism based on density functional theory calculations, and the versatility of these entities is highlighted through post-functionalization reactions.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Morgane Sayes, Guillaume Benoit, Andre B. Charette
Article
Chemistry, Multidisciplinary
Xuemei Liu, Chaonan Cui, Shuoshuo Wei, Jinyu Han, Xinli Zhu, Qingfeng Ge, Hua Wang
Summary: This study presents a new strategy for designing efficient photocatalysts that can convert CO2 into hydrocarbons by utilizing synergistic catalytic sites. The findings provide a solution for the selective photocatalytic reduction of CO2 to CH4.
Article
Chemistry, Multidisciplinary
Chengxian Hu, Dan Wang, Lu Wang, Ying Fu, Zhengyin Du
Summary: A novel one-pot, three-component reaction conducted under electrochemical conditions was studied. The reaction involved 2-aminothiophenols, aldehydes, and malononitrile, using TBABF4 as an electrolyte and CuI as a catalyst. The proposed reaction mechanism suggested that CuI served as an electron relay. This method offers simplified operation, high atom economy, and mild reaction conditions.
Article
Chemistry, Multidisciplinary
Zhi Yang, Yu Chen, Linxi Wan, Yuxiao Li, Dan Chen, Jianlin Tao, Pei Tang, Fen-Er Chen
Summary: A highly enantioselective method for the complete hydrogenation of pyrimidinium salts using Ir/(S,S)-f-Binaphane complex as the catalyst was developed. This method provides easy access to fully saturated chiral hexahydropyrimidines, which are prevalent in many bioactive molecules. The reactions exhibit high yields and enantioselectivities under mild reaction conditions without additives. Successful application of this methodology in a continuous flow fashion further extends its practical utility.
Article
Chemistry, Multidisciplinary
Tina Jeoh, Jennifer Danger Nill, Wujun Zhao, Sankar Raju Narayanasamy, Liang Chen, Hoi-Ying N. Holman
Summary: In this study, the enzymatic hydrolysis of cellulose was investigated using real-time infrared spectromicroscopy. The spatial heterogeneity of cellulose was found to impact the hydrolysis kinetics. Hydration affected cellulose ordering, and Cel7A preferentially removed less extensively hydrogen bonded cellulose.
Article
Chemistry, Multidisciplinary
Tiphaine Richard, Walid Abdallah, Xavier Trivelli, Mathieu Sauthier, Clement Dumont
Summary: An effective method of grafting functionalities onto lignin based on glycerol carbonate has been developed using an efficient nickel-catalysed telomerisation reaction. This method allows lignin to have new reactive functions and reduces the glass transition temperatures of modified lignins, thereby expanding the application range of lignin-based resins.
Article
Chemistry, Multidisciplinary
Jing Qi, Xiyan Wang, Gan Wang, Srinivas Reddy Dubbaka, Patrick ONeill, Hwee Ting Ang, Jie Wu
Summary: This study presents a green and environmentally friendly approach for the synthesis of imides using electrocatalytic oxidation with H2O as the oxygen source. The method eliminates the need for toxic or expensive oxidants and achieves high yields under mild reaction conditions. It shows broad substrate compatibility and potential for industrial applications.
Article
Chemistry, Multidisciplinary
Babasaheb Sopan Gore, Lin-Wei Pan, Jun-Hao Lin, Yi-Chi Luo, Jeh-Jeng Wang
Summary: Here, we report a visible light-promoted intramolecular radical cascade reaction for the construction of fluorenol and naphthalene-fused cyclopropyl carbaldehyde derivatives. This method offers mild reaction conditions, a broad substrate scope, excellent step efficiency, and scalability, without the need for external chemical oxidants. The novelty of this protocol was demonstrated by synthesizing chrysene analogs and performing late-stage functionalizations.
Article
Chemistry, Multidisciplinary
Juho Antti Sirvio, Idamaria Romakkaniemi, Juha Ahola, Svitlana Filonenko, Juha P. Heiskanen, Ari Ammala
Summary: This article discusses the method of using supramolecular interaction between an aromatic hydrogen bond donor and lignin to achieve rapid delignification of softwood at low temperatures.
Article
Chemistry, Multidisciplinary
Yunyan Meng, Chunxiang Pan, Na Liu, Hongjiang Li, Zixiu Liu, Yao Deng, Zixiang Wei, Jianbin Xu, Baomin Fan
Summary: A novel visible light-driven synthesis method for 2,3-diamines has been developed, which has mild conditions, avoids the use of metal reagents, and can synthesize diamines and diols in one pot.
Article
Chemistry, Multidisciplinary
Mingqing Huang, Haiyang Huang, Mengyao You, Xinxin Zhang, Longgen Sun, Chao Chen, Zhichao Mei, Ruchun Yang, Qiang Xiao
Summary: A direct air-oxidized strategy for the synthesis of benzo[b]phosphole oxides was developed in this study. Arylphosphine oxides were transformed into phosphinoyl radicals, which were further combined with various alkynes to achieve the desired products. DFT calculations revealed the mechanism of phosphinoyl radical formation.
Article
Chemistry, Multidisciplinary
Anwei Wang, Jiayin Huang, Chunsheng Zhao, Yu Fan, Junfeng Qian, Qun Chen, Mingyang He, Weiyou Zhou
Summary: This study demonstrates an innovative strategy for the aerobic oxidation of C(sp(3))-H bonds using gamma-valerolactone. By optimizing the reaction conditions and utilizing specific catalysts, efficient oxidation of C(sp(3))-H bonds is achieved with good chemoselectivity in certain cases.
Article
Chemistry, Multidisciplinary
Shun Li, Likai Tong, Zhijian Peng, Bo Zhang, Xiuli Fu
Summary: Sulfide compounds show promise as electrocatalysts for water splitting, but their performance is limited by factors such as limited active sites and hindered substance transport. This study successfully prepared a high-entropy sulfide (ZnCoMnFeAlMg)(9)S-8, which reduced grain size and increased specific surface area, enabling the realization of a dual-functional catalyst with multiple catalytic sites. High entropy also modulated the electronic properties of sulfides, reducing the potential energy barrier for hydrolysis. This research introduces a new approach for functionalizing high entropy nanomaterials and improves the performance of water splitting catalysts.
