Article
Chemistry, Applied
Lyudmila A. Grishchenko, Lidiya N. Parshina, Lyudmila I. Larina, Yana A. Kostyro, Boris A. Trofimov
Summary: New salicylate derivatives of arabinogalactan have been synthesized with high yield, showing high anti-coagulation activity. The reaction yield varies depending on the base used, and unexpected additional reactions were observed in the presence of piperidine.
CARBOHYDRATE POLYMERS
(2021)
Article
Chemistry, Inorganic & Nuclear
Gilian T. Thomas, Kiera Ronda, J. Scott McIndoe
Summary: The cross-coupling of N-tosylhydrazones and aryl halides to form carbon-carbon bonds, producing 1,1-disubstituted alkenes, has been widely used in chemistry, but its mechanism remains experimentally unexplored. The combination of benchtop NMR and real-time mass spectrometry allows for monitoring of catalytic intermediates and the rate of product formation.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Organic
Swati Jain, Ruchi Anmol, Ruchi Sharma, Tarak Karmakar, M. Ramu Yadav
Summary: We have developed an efficient Cu/N,N-bidentate imine ligand catalytic system for C(sp(3))-C(sp) coupling, which can synthesize internal alkynes, di/trisubstituted allenes, and strained bridged cyclic lactams in moderate to excellent yields from readily available alkyl(benzyl) bromides. Density Functional Theory (DFT) assisted mechanistic study and control experiments support the involvement of bialkynylated copper species in the reaction, which undergoes single electron transfer (SET) with alkyl halides to generate radical intermediates. The N,N-bidentate imine ligand plays a crucial role in stabilizing the intermediate copper complex and facilitating product formation.
Article
Chemistry, Physical
Aonan Zhu, Shu Niu, Cancan Zhang, Yonglong Li, Aoxuan Du, Wei Xie
Summary: The study investigates the superior performance of bimetallic nanocatalysts compared to monometallic analogues. By using surface-enhanced Raman spectroscopy, it is found that the exceptional performance of bimetallic nanocatalysts in the Sonogashira cross-coupling reaction is due to the positive crowding-out effect of active Pd species. The effect is regulated by the doping of Ni, as demonstrated by X-ray photoelectron spectroscopy and density functional theory calculations.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Gang Wang, Pengcheng Hao, Yajuan Chang, Qiuping Zhang, Wanyi Liu, Bin Duan, Haijuan Zhan, Shuxian Bi
Summary: Modified polyaniline self-stabilizing Cu/Pd bimetallic sub-nanocluster composite materials obtained through oxidative polymerization, structural modification, and metal self-trapping show excellent catalytic performance.
Article
Chemistry, Physical
Antonio Torres-Calis, Diego A. Roa, Juventino J. Garcia
Summary: We developed a manganese-catalyzed method for the synthesis of secondary amines by reductively coupling nitroarenes and alkenes. The protocol showed high efficiency and simplicity, utilizing commercially available reagents. Styrenes, which are challenging substrates, achieved excellent to moderate yields under this strategy. Mechanistic studies revealed a homogeneous system operating through a radical pathway, with carbon-centered radical and nitroso species as key reactive intermediates.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Physical
Yiwei Zhou, Jian Zhao
Summary: By utilizing CuxO nanoparticles supported on carbon nanotube as catalyst, visible light efficiently transforms Glaser homo-coupling into Sonogashira cross-coupling with high product selectivity. The active species under light irradiation is different from that in the dark, and the synergistic effect between Cu(II) and Cu(I) enhances the Glaser product yield in the dark.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2022)
Article
Chemistry, Multidisciplinary
Ding-Wei Ji, Yan-Cheng Hu, Xiang-Ting Min, Heng Liu, Wei-Song Zhang, Ying Li, Yongjin J. Zhou, Qing-An Chen
Summary: This study demonstrates a unique skeleton-reorganizing coupling reaction of cycloheptatriene and cycloalkenones with amines. The reaction selectively couples cycloheptatriene with anilines to deliver fused 1,2-dihydroquinoline products in the presence of Rh/acid catalysis. Mechanistic studies reveal that the ring reorganization occurs through retro-Mannich type ring-opening and subsequent intramolecular Povarov reaction. The synthetic utilization of this reaction is showcased with gram-scale reaction, synthetic derivatizations, and late-stage modification of commercial drugs.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Tohru Kamitanaka, Yusuke Tsunoda, Yuriko Fujita, Toshifumi Dohi, Yasuyuki Kita
Summary: The synthesis of 2-oxygenated dihydrobenzofurans via [3 + 2] coupling of quinone monoacetals with vinyl ethers has been achieved using tetrabutylammonium triflate catalysis. This new method involves activating the acetal moiety in quinone monoacetals under acid-free conditions to obtain highly oxygenated dihydrobenzofurans, with triflate anion catalyst stabilizing the cationic intermediate.
Article
Chemistry, Inorganic & Nuclear
Tobias Kaper, Connor W. W. Frye, Ian A. A. Tonks
Summary: This study examines the potential of allenes as selective coupling partners in a Ti-catalyzed [2 + 2 + 1] pyrrole synthesis reaction. The results show that 1,2-cyclononadiene acts as a regioselective insertion coupling partner, producing 2,3-annulated pyrroles through reaction with alkynes and azobenzene. Additionally, propadiene undergoes both [2 + 2] cycloaddition and insertion in a highly regioselective manner, yielding exclusively N-phenyl-2,5-dimethylpyrrole, while propyne results in an unselective regioisomeric mixture. This highlights the complementary or better selectivity provided by allenes compared to alkynes in multicomponent synthesis.
Article
Chemistry, Physical
Xiaojun Zeng, Chao Wang, Wenhao Yan, Jian Rong, Yanshan Song, Zhiwei Xiao, Aijie Cai, Steven H. Liang, Wei Liu
Summary: Despite the historical challenge of engaging unactivated alkyl halides in Sonogashira coupling reactions, we have developed a strategy that combines Cu-catalyzed alkyne transfer with aryl radical activation of carbon-halide bonds. This allows for a general approach to coupling alkyl iodides with terminal alkynes. This unprecedented reaction tolerates a wide range of functional groups and has been applied to the late-stage cross-coupling of pharmaceutical agents and the synthesis of positron emission tomography tracers.
Article
Chemistry, Physical
Xiaojun Zeng, Chao Wang, Wenhao Yan, Jian Rong, Yanshan Song, Zhiwei Xiao, Aijie Cai, Steven H. Liang, Wei Liu
Summary: A new strategy combining Cu-catalyzed alkyne transfer with aryl radical activation of carbon-halide bonds enables the coupling of alkyl iodides with terminal alkynes. This unprecedented Sonogashira-type cross coupling reaction is tolerant towards a wide range of functional groups and has applications in pharmaceutical synthesis and the synthesis of positron emission tomography tracers.
Article
Chemistry, Multidisciplinary
Jessica S. Graham, Harriet A. Stanway-Gordon, Michael J. Waring
Summary: DNA-Encoded Libraries (DELs) are widely used as a hit identification strategy for drug discovery campaigns. The success of DELs relies on efficient reactions that can be carried out on DNA. The Sonogashira coupling is an important reaction for on-DNA chemistry, allowing the efficient coupling of alkynes to aryl halides. Our micellar technology provides highly efficient conversions for the Sonogashira reaction, enabling the synthesis of diverse DELs.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Medicinal
Adrian Krzyzanowski, Axel Pahl, Michael Grigalunas, Herbert Waldmann
Summary: The spatial score (SPS) is an empirical scoring system that expresses the spatial complexity of a compound in a uniform and granular manner. It can differentiate natural products and synthetic compounds and is applicable in the analysis of biological activity data.
JOURNAL OF MEDICINAL CHEMISTRY
(2023)
Article
Chemistry, Organic
Yoshihiko Morimoto, Moe Hamada, Shotaro Takano, Katsufumi Mochizuki, Takuya Kochi, Fumitoshi Kakiuchi
Summary: Utilizing 8-quinolinolato rhodium catalysts and CsF, the coupling of alkylacetylenes with secondary amines in both 2:1 and 1:1 ratios was achieved. The solvent choice can switch the selectivity between 2:1 and 1:1 ratios, leading to different products under different reaction conditions.Additionally, anti-Markovnikov hydroamination reactions in toluene resulted in 1:1 coupling products under relatively mild conditions.
Article
Chemistry, Organic
Jessica Liyu, Shi-Wei Kim, Tilo Sohnel, Jonathan Sperry
Summary: Efforts towards a biomimetic synthesis of alkaloid pegaharmaline A discovered a potential alternative biosynthetic pathway and the need for structural revision of the natural product.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Maurycy Prystupa, Tilo Sohnel, Jonathan Sperry
Summary: This study reports a method for synthesizing the putative bisindigotin structure by strategically ordering oxidative dimerization, reduction, and dehydration events, as well as a rearrangement method using p-TSA.
TETRAHEDRON LETTERS
(2022)
Article
Engineering, Environmental
Kapish Gobindlal, Zoran Zujovic, Jacob Jaine, Cameron C. Weber, Jonathan Sperry
Summary: Perfluorosulfonic acids (PFSAs), a subclass of PFASs, can be effectively destroyed through mechanochemical destruction (MCD) in the presence of quartz sand (SiO2), without the need for solvents and under ambient conditions. The destruction efficiency of five different PFSAs subjected to MCD conditions with SiO2 reached 99.95% to 100%. Other PFASs were formed and ultimately destroyed during the degradation process. Solid-state nuclear magnetic resonance spectroscopy confirmed the formation of silicon-fluorine (Si-F) bonds post-MCD, indicating the stable sequestration of fluorine.
ENVIRONMENTAL SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Organic
Simon X. Lin, Lachlan M. Blair, Tilo Sohnel, Jonathan Sperry
Summary: The synthesis of the spirobisindole core of the [5,5]-spiroindimicin alkaloids through Fischer indolisation between a cyclopenta[b]indole-3-carbaldehyde and phenylhydrazine did not proceed as expected, resulting in the formation of a cyclopenta[c]pyrazole instead. Further investigation revealed that this unusual rearrangement reaction has a wide range of applications and provides a straightforward method to access this heteroaromatic motif.
TETRAHEDRON LETTERS
(2023)
Review
Chemistry, Multidisciplinary
Daniel G. Anstis, Jessica Liyu, Emma K. Davison, Jonathan Sperry
Summary: The plant Peganum harmala contains 160 alkaloids, most of which have no reported bioactivity. Although classic entheogens have not been found, these structurally unique alkaloids may contribute to the discovery of new entheogenic substances.
AUSTRALIAN JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Organic
Yihan Yu, Jonathan Sperry
Summary: This study successfully synthesized a rare structure in marine algae and elucidated the biosynthetic pathway of its natural product through synthesis.
TETRAHEDRON LETTERS
(2023)
Article
Chemistry, Organic
Karen Ichikawa, Jessica C. Neville, Yihan Yu, Jonathan Sperry
Summary: In this study, a synthetic strategy for the marine alkaloid convolutindole A was reported, and an iterative C-H functionalization strategy was found to be more successful. The utility of the iridium-catalyzed C-H borylation methodology in preparing densely functionalized indoles was showcased, providing a foundation for ongoing synthetic efforts.
TETRAHEDRON LETTERS
(2023)
Article
Chemistry, Organic
Hannah M. Johnson, Tilo Sohnel, Jonathan Sperry
Summary: This paper reports a short synthesis of phragmunis A and highlights the differences between the synthetic sample and the natural product. The lack of an authentic sample and NMR spectra for the natural product has hindered the structural re-assignment of phragmunis A, leaving its correct structure a mystery.
TETRAHEDRON LETTERS
(2023)
Article
Chemistry, Organic
Simon X. Lin, Jonathan Sperry
Summary: The synthesis of lysiformine, a bisindole alkaloid, was described. The heterocyclic framework of the natural product was assembled using iterative Suzuki coupling and reductive alkylation reactions starting from a pyridine derived from kojic acid. NMR spectroscopic analysis confirmed that the synthetic sample matched well with the natural product, highlighting the rarity of a marine natural product containing a 3-hydroxypyridine.
TETRAHEDRON LETTERS
(2023)
Article
Chemistry, Physical
Binglin Chen, Zhendong Yu, Renjie Huang, Ye Tian, Zheng Li, Jonathan Sperry, Shuliang Yang, Xing Tang, Yong Sun, Lu Lin, Xianhai Zeng
Summary: This study reports the synthesis of 2,5-hexanedione (HD) from 5-(chloromethyl)furfural (CMF) using polymethylhydrosiloxane (PMHS) as the hydrogen donor for the first time. It was found that the yield of HD reached 78% at 160°C for 30 minutes. The presence of acidic protons significantly promoted the coupling reaction (hydrodechlorination, hydrogenolysis, and hydrolysis) from a kinetic and thermodynamic perspective. Modifying Pd nanoparticles (NPs) with in situ generated Cl species improved the adsorption of substrate molecules on step sites compared to corner sites. This work provides insights into the role of acidic protons and the migration mechanism of Cl species, and offers a basis for the development of future catalytic systems and the synthesis of biomass-derived chemicals.
Article
Chemistry, Multidisciplinary
Emma K. Davison, Jessica C. Neville, Jonathan Sperry
Summary: Phosphorus compounds are essential in modern society, but their sourcing from phosphate rock is energy intensive and inefficient. With the depletion of phosphate rock deposits, alternative sources of phosphorus such as phytic acid (PA) should be explored. PA, considered an agricultural waste, has attractive features like being non-toxic, abundant, and in a redox efficient state. Furthermore, the use of PA as a commodity platform could reduce phosphorus flow into the environment.
Article
Chemistry, Organic
Juan J. Arteaga J. Giraldo, Ashley C. Lindsay, Rachel Chae-Young Seo, Paul A. Kilmartin, Jonathan Sperry
Summary: 2-Oxindoles are commonly found heteroaromatic motifs in natural products and pharmaceuticals. A feasible method for synthesizing 2-oxindoles is by oxidizing the corresponding indoles, which currently involves the use of stoichiometric amounts of unsafe chemical oxidants and can lead to the formation of unwanted by-products. In this study, we found that 3-substituted indoles can be electrochemically oxidized to the corresponding 2-oxindoles in the presence of potassium bromide, with only minimal formation of oxidative dimers. The reaction proceeds through the electrochemical generation of bromine, which reacts with indole and undergoes hydrolysis to yield the desired 2-oxindole. This procedure offers an attractive alternative to existing methods for accessing 2-oxindoles by oxidation of indoles.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Engineering, Environmental
Kapish Gobindlal, Erin Shields, Andrew Whitehill, Cameron C. Weber, Jonathan Sperry
Summary: This study demonstrates that mechanochemical destruction (MCD) is an effective method for the destruction of PFASs in AFFF concentrate and PFAS-contaminated soil. Both targeted and non-targeted analysis were used to evaluate the degradation of PFASs during MCD treatment, showing high destruction efficiencies. The use of MCD could be a viable option for remediation of PFAS-contaminated land and destruction of stockpiled AFFFs.
ENVIRONMENTAL SCIENCE-ADVANCES
(2023)
Article
Chemistry, Organic
Stephanie Lee, Tilo Sohnel, Jonathan Sperry
Summary: In this study, unexpected results emerged during the synthetic study of the unique triazocane present in hicksoane alkaloids. The mechanisms behind the formation of the reaction products were elucidated through control reactions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Jessica C. Neville, Michelle Y. Lau, Tilo Sohnel, Jonathan Sperry
Summary: Chitin-derived platforms have emerged as valuable chemical entities for nitrogenous fine chemicals construction independent of the Haber ammonia process. However, much of the research in this field has focused on achiral platforms, limiting the access to enantiopure, bio-based nitrogenous chemical space. In this study, dihydroxyethyl acetamidofuran (Di-HAF), a chiral synthon easily available from chitin, has been transformed into epi-leptosphaerin, a marine alkaloid. This work extends the concept of Haber-independent synthesis to enantiopure chemical space that is not routinely accessible from existing achiral platforms.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
