Article
Chemistry, Organic
Zhi-Long Jia, Xian-Tao An, Yu-Hua Deng, Lin-Han Pang, Chun-Fang Liu, Le-Le Meng, Jia-Kun Xue, Xian-He Zhao, Chun-An Fan
Summary: An unprecedented asymmetric catalytic (4 + 2) annulation reaction has been developed for the synthesis of chiral cyclohexadienone-fused cyclohexyl spirooxindoles using aryl-substituted gamma-methylidene-delta-valerolactones (GMDVs) and isatin-derived para-quinone methides (p-QMs) catalyzed by palladium(0) and (S,S,S)-(-)-Xyl-SKP. This reaction can efficiently and selectively forge three highly congested contiguous tetrasubstituted carbon atoms, including two vicinal quaternary stereogenic centers.
Article
Chemistry, Organic
Ran Song, Zhendong Lian, Wei Feng, Tianyi Guan, Wen Si, Daoshan Yang, Jian Lv
Summary: A novel palladium-catalyzed decarboxylative O-allylation of phenols was developed. A gamma-methylidene-delta-valerolactone (GMDV) was identified as an efficient and selective allylation reagent, leading to the synthesis of allyl phenyl ethers in high yields under mild conditions.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Can Gao, Ting Zhang, Xiaoxun Li, Jing-De Wu, Jitian Liu
Summary: A new asymmetric reaction strategy for the synthesis of enantiomerically enriched and polycyclic molecules has been reported. By using a newly designed catalyst, high yields and high selectivities were achieved. This method offers mild reaction conditions and good functional group tolerance, making it important for the synthesis of organic compounds.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Can Li, Zhengnan Zhou, Yuling Li, Yinlong Guo, Shengming Ma
Summary: The reactivity of a novel organometallic intermediate, vinylidene-pi-allyl palladium species, has been demonstrated, showing its ability to react with 4-alken-2-ynyl carbonates and stabilized carbon nucleophiles to produce functionalized 1,2,3,-butatriene compounds with moderate to high yields and excellent regioselectivities.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Shu-Pei Yuan, Qing Bao, Ting-Jia Sun, Jian-Qiang Zhao, Zhen-Hua Wang, Yong You, Yan-Ping Zhang, Ming-Qiang Zhou, Wei-Cheng Yuan
Summary: A palladium-catalyzed enantioselective alpha-allylation reaction has been developed, leading to the synthesis of a series of nitrogen-containing compounds with an all-carbon quaternary stereocenter. The method demonstrated high yields and excellent enantioselectivities, and its utility was showcased through large-scale reactions and synthetic transformations of the products.
Article
Chemistry, Organic
Camilla Loro, Julie Oble, Francesca Foschi, Marta Papis, Egle M. Beccalli, Sabrina Giofre, Giovanni Poli, Gianluigi Broggini
Summary: Treatment of O-allyl N-tosyl carbamates with aromatic compounds in the presence of Cu(OTf)(2) or TMSOTf as promoters results in the formation of N-substituted 1-arylpropan-2-amines, 1,2-diarylpropanes, 1,1-diarylpropanes, or indanes, depending on the nature of the promoter and aryl substrates. A proposed mechanism explains the outcome of these C-H based cascades, involving initial acid promoted decarboxylative/deamidative Friedel-Crafts allylation followed by protonation of the allylated arene.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Review
Chemistry, Organic
Ben Niu, Yin Wei, Min Shi
Summary: In recent years, Pd-catalyzed annulation reactions using zwitterionic pi-allyl palladium intermediates have been extensively studied, demonstrating their importance in the synthesis of carbocyclic and heterocyclic compounds with potential pharmaceutical and biological applications. This review highlights the significant advances in organic synthesis based on zwitterionic pi-allyl palladium and propargyl palladium.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Physical
David Vesseur, Marte S. M. Holmsen, Didier Bourissou
Summary: p-Allyl complexes of transition metals play important roles in organometallic chemistry and homogeneous catalysis. Palladium(II) p-allyl complexes have received much attention, while their isoelectronic gold(III) counterparts were difficult to obtain. However, this has changed in recent years. This concept article discusses the preparation, characterization, structure, and reactivity of these complexes, as well as their catalytic applications. The influence of the ancillary ligand at gold is analyzed in detail, comparing the similarities and differences with the Pd(II) p-allyl complexes.
Article
Chemistry, Multidisciplinary
Juan Du, Yun-Fan Li, Chang-Hua Ding
Summary: Palladium-catalyzed cycloaddition reactions using Pd-p-allyl zwitterions are significant synthetic transformations for the construction of carbon- or heterocycles compounds found in biologically active natural products and pharmaceuticals. Recent studies have explored new applications of previously less-studied Pd-p-allyl zwitterions and designed impressive novel zwitterions, which are diverse and highly reactive intermediates for the synthesis of complex polycyclics and medium-sized cyclic compounds.
CHINESE CHEMICAL LETTERS
(2023)
Article
Chemistry, Organic
Ashok Donthoju, Anandarao Munakala, Sushma Ellandula, Rambabu Chegondi
Summary: In this study, we have reported a palladium(0)-catalyzed decarboxylative oxa-Michael addition/remote alpha-allylation/1,3-migration reaction with high yields. The reaction is triggered by a base-mediated retro-Michael ring-opening reaction and subsequent syn-selective oxa-Michael addition.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Bastian Jakob, Ichraf Slimani, Andreas Diehl, Naceur Hamdi, Georg Manolikakes
Summary: This study presents a palladium-catalyzed decarboxylative 1,2-addition of carboxylic acids to glyoxylic acid esters, providing access to the mandelic acid scaffold in good yields. The method utilizes readily available benzoic acids as a more sustainable alternative to preformed organometallic nucleophiles, showing promise for environmentally friendly organic synthesis.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Mario Prejano, Raffaella Mancuso, Tiziana Marino, Bartolo Gabriele
Summary: In this study, a detailed computational investigation was conducted on the conversion of 1-(methylthio)-3-yn-2-ols to thiophene-3-carboxylate esters using PdI2/KI catalyst. The study provides insights into the role of each species involved in the reaction mechanism and confirms the experimental data.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Kuan Li, Sen Yang, Bing Zheng, Wei Wang, Yongjun Wu, Jing Li, Hongchao Guo
Summary: In this study, a new type of delta-vinylvalerolactone was designed and synthesized as a precursor in Pd-catalyzed [6+3] cycloaddition. The reaction resulted in nine-membered 1,2-dinitrogen-containing heterocycles in high yields with excellent diastereoselectivity. Further transformation of these ring-fused products led to the formation of unusual tetracyclic bridged-ring compounds without loss of diastereoselectivity.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Cun Yang, Zhi-Xiong Yang, Chang-Hua Ding, Bin Xu, Xue-Long Hou
Summary: The personal account summarizes the development of new dipolarophiles comprising electron-deficient alkenes, allenes, and alkynes for Pd-catalyzed asymmetric cycloaddition reactions, showcasing their efficiency and selectivity in synthesizing compounds with contiguous chiral centers. Additionally, the study reveals dissimilar reactivity of different electron deficient alkenes and explains the mechanism and stereo-control of the reaction, along with disclosing a Pd-catalyzed inverse [3+2] cycloaddition.
Article
Chemistry, Organic
Dong-Chao Wang, Pan-Pan Wu, Pei-Yu Du, Gui-Rong Qu, Hai-Ming Guo
Summary: A palladium-catalyzed domino Heck/decarboxylative alkynylation reaction has been developed for the synthesis of 3,3-disubstituted oxindoles and hydropyrimidinyl spirooxindoles from trisubstituted alkenes or enamines. The reaction showed good yields and demonstrated its wide applicability through gram-scale syntheses and diverse transformations of the reaction products. The enantioselective version of the reaction was also investigated.
Article
Chemistry, Multidisciplinary
Shubham Mishra, Soyoung Park, Tomoko Emura, Hidaka Kumi, Hiroshi Sugiyama, Masayuki Endo
Summary: Stimuli-responsive switching molecules such as arylazopyrazole (AAP) have shown promising potential in controlling photoinduced assembly and disassembly of DNA origami nanostructures. AAP can achieve repeated assembly and disassembly of DNA origami structures through alternating UV and visible-light irradiation, demonstrating its versatility as a photoswitching molecule.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Materials Science, Biomaterials
Ji Hye Yum, Takumi Ishizuka, Koyuki Fukumoto, Daisuke Hori, Hong-Liang Bao, Yan Xu, Hiroshi Sugiyama, Soyoung Park
Summary: Chemical modifications of innate DNA/RNA aptamers can improve their function. This study demonstrates a modular strategy to manipulate a thrombin-binding DNA aptamer by incorporating amino acid conjugates to enhance anticoagulation activity and binding affinity. The research findings reveal that substitutions with hydrophobic amino acids in the loop region can significantly increase antithrombin activity.
ACS BIOMATERIALS SCIENCE & ENGINEERING
(2021)
Article
Biochemical Research Methods
Takuya Hidaka, Wen Ann Wee, Ji Hye Yum, Hiroshi Sugiyama, Soyoung Park
Summary: This study induced phase transition of micro-compartments containing DNA and polylysine by modulating duplex formation of arylazopyrazole-conjugated oligonucleotides with light. UV irradiation destabilized DNA duplex and generated isotropic coacervates, while visible light irradiation caused the formation of liquid crystalline coacervates. This photocontrol of phase transition was highly repeatable, and similar changes were observed even after ten cycles of light irradiation.
BIOCONJUGATE CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Daisuke Hori, Ji Hye Yum, Hiroshi Sugiyama, Soyoung Park
Summary: G-quadruplex (G4) is a well-known noncanonical conformation of DNA with important roles in pharmacological and biological contexts. Tropylium derivatives have been found to effectively bind with G4s, showing potential for future applications in cellular environments.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2021)
Article
Materials Science, Multidisciplinary
Md. Kaiser Haider, Lei Sun, Azeem Ullah, Sana Ullah, Yuji Suzuki, Soyoung Park, Yo Kato, Yasushi Tamada, Ick Soo Kim
Summary: The study fabricated composite nanofibrous scaffolds from blends of PAN, nCB, and HA via electrospinning to observe the effect of nCB on membrane properties. The results showed that the addition of nCB reduced the average diameter of nanofibers and improved the mechanical performance of the scaffold. Excellent mineralization and biocompatibility were observed, indicating strong potential for use as bone and hard tissue restoring materials.
MATERIALS TODAY COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Mengqin Liu, Yixiao Cui, Yaping Zhang, Ran An, Lin Li, Soyoung Park, Hiroshi Sugiyama, Xingguo Liang
Summary: This study investigated the formation of Z-DNA conformation using a fluorescent nucleobase and found that Z-DNA can be formed in Z-B-chimera under low ionic strength conditions, with more difficulty at lower pH.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2022)
Article
Biochemistry & Molecular Biology
Yusuke Kawamoto, Wen Liu, Ji Hye Yum, Soyoung Park, Hiroshi Sugiyama, Yuki Takahashi, Yoshinobu Takakura
Summary: The study designed and synthesized covalent DNA dendrons bearing multivalent cytosine-phosphate-guanine oligodeoxynucleotides (CpG ODNs), which can stimulate the immune system by activating TLR9. These dendrons showed higher resistance to nuclease degradation than linear ODNs and were more efficiently taken up by macrophage-like cells. The enhanced immune-stimulating properties of covalent DNA dendrons were demonstrated through increased secretion of proinflammatory cytokines.
Article
Biochemistry & Molecular Biology
Ryu Tashiro, Ji Hye Yum, Soyoung Park, Hiroshi Sugiyama
Summary: The study showed that the photoreactivity of U-Br changes dramatically from hydrogen abstraction to cross-linking by changing the conformation of the duplex from the B-form to the A-form. Among three A-form structures, the largest amount of cross-linked products was observed when U-Br was incorporated into the RNA strand and the pyrene was conjugated to the 5 ' end of the DNA. These results indicate that the contact manner of pyrene was different between A- and B-form duplexes.
Article
Multidisciplinary Sciences
Wen Ann Wee, Hiroshi Sugiyama, Soyoung Park
Summary: This study demonstrates the light-controlled formation and disassembly of liquid droplets composed of a complex of polylysine and arylazopyrazole-conjugated single-stranded DNA, showing potential for regulating chemical reactions through dynamic LLPS.
Article
Biochemistry & Molecular Biology
Shingo Hirashima, Hiroshi Sugiyama, Soyoung Park
Summary: This study characterized 2FA-containing DNA molecules and found that they have similar structure and properties to native adenine due to their small size, but exhibit unique features due to their high electronegativity. This provides valuable information for future applications of 2FA-modified DNA.
Review
Chemistry, Multidisciplinary
Ji Hye Yum, Hiroshi Sugiyama, Soyoung Park
Summary: Since the first report of DNAzyme by in vitro selection in 1994, the study and application of catalytic DNA has been extensively explored. The use of DNA as a catalyst in asymmetric synthesis has attracted attention due to its potential for green and sustainable applications.
Article
Chemistry, Multidisciplinary
Shingo Hirashima, Soyoung Park, Hiroshi Sugiyama
Summary: Forster resonance energy transfer (FRET) is a useful tool for understanding biomolecular dynamics, and FRET-based analysis of nucleosomes has the potential to bridge the gap between static structures and dynamic cellular behaviors. Nucleoside-based FRET pairs offer advantages over traditional pairs, as they can be incorporated into the helical structures of nucleic acids. This study investigates the construction of nucleosomes with nucleobase FRET pairs and analyzes experimental and theoretical FRET efficiencies using fluorescence spectroscopy and molecular dynamics simulations, respectively. The results show distinguishable experimental FRET efficiencies depending on the positions of FRET pairs in nucleosomal DNA, which are supported by theoretical calculations. This research suggests the possibility of using this approach to analyze structural changes in nucleosomes caused by epigenetic modifications or internucleosomal interactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Tomotaka Kumagai, Ban Kinoshita, Shingo Hirashima, Hiroshi Sugiyama, Soyoung Park
Summary: Fluorescent molecular rotors are versatile tools for investigating biomolecular interactions and monitoring microenvironmental changes. We report the synthesis and characterization of a highly emissive molecular rotor-containing thymine nucleoside and its analogue, which can emit vivid fluorescence via interaction with target proteins. These probes have the potential to serve as robust tools for fluorescence mapping and monitoring specific protein-binding interactions in biological systems.
Article
Chemistry, Multidisciplinary
Ji Hye Yum, Tomotaka Kumagai, Daisuke Hori, Hiroshi Sugiyama, Soyoung Park
Summary: In this study, Cu-histidine (His)-DNA hybrids were constructed as laccase-mimetic DNAzymes. The Cu-His-DNAzymes exhibited remarkable activity in a colorimetric oxidation reaction between 2,4-dichlorophenol and 4-aminoantipyrine. Our findings provide new insights for the systematic construction of tailor-made active sites for biomimetics.
Article
Biochemistry & Molecular Biology
Wen Ann Wee, Ji Hye Yum, Shingo Hirashima, Hiroshi Sugiyama, Soyoung Park
Summary: This study presents a bifunctional trifluoromethylphenylpyrrolocytidine derivative ((FP)dC) as a dual-purpose probe for both fluorescence and F-19 NMR spectroscopic DNA analysis. The research successfully investigated the noncanonical DNA structure i-motifs through changes in fluorescence intensity and F-19 chemical shift using (FP)dC-containing DNA.
RSC CHEMICAL BIOLOGY
(2021)
