Article
Chemistry, Organic
Samar Bou Zeid, Samar Eid, Fadia Najjar, Aurelie Mace, Ivan Rivilla, Fernando P. Cossio, Vincent Dorcet, Thierry Roisnel, Francois Carreaux
Summary: The effect of microwave irradiation on the 1,3-Dioxa-[3,3]-sigmatropic rearrangement of aryl allylic carbamates was investigated, showing faster reaction acceleration and similar or improved yields compared to conventional heating conditions. This experimental improvement extended the diversity of carbamates able to undergo this rearrangement, and a synthetic pathway to access new heterocyclic structures was successfully developed. DFT and Fragment Distortion studies demonstrated polar transition structures with lower activation barriers.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Norie Momiyama, Yasushi Honda, Toshiyasu Suzuki, Chanantida Jongwohan
Summary: The mechanism of Bronsted acid-initiated formal [1,3]-rearrangement was rationalized using density functional theory (DFT) calculations, revealing a highly reactive intermediate and the real catalyst species. The computational study provided important mechanistic insights and guided the design of chiral catalysts for rearrangement process.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Zhonghong Chen, Min Tan, Chunhui Shan, Xiaoling Yuan, Liyuan Chen, Jiarong Shi, Yu Lan, Yang Li
Summary: In this study, both aryne 1,4-disubstitution and 1,2,4-trifunctionalization were achieved by using tertiary amines with a penta-2,4-dien-1-yl moiety. The reactions resulted in the incorporation of a C-N and a C-C bond para to each other on an aryne intermediate through sequential nucleophilic addition and [5,5]-sigmatropic rearrangement. When arynes with 3-tethered electrophiles were used, a cascade regioselective nucleophilic addition, intramolecular cyclization, and remote diastereoselective [5,5]-sigmatropic rearrangement process were observed. Density functional theory (DFT) calculations revealed that the remote diastereoselective control in this reaction system is due to hydrogen-bonding interactions between two C-H hydrogens on the penta-2,4-dien-1-yl chain and the oxygen anion generated upon N-nucleophilic annulation reaction in the [5,5]-sigmatropic rearrangement step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Shutaro Karashima, Alexander Humeniuk, Ryuta Uenishi, Takuya Horio, Manabu Kanno, Tetsuro Ohta, Junichi Nishitani, Roland Mitric, Toshinori Suzuki
Summary: The photoinduced ring-opening reaction of 1,3-cyclohexadiene to produce 1,3,5-hexatriene plays a crucial role in the photobiological synthesis of vitamin D-3, following the Woodward-Hoffmann rule and proceeding via nonadiabatic transitions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Xin Liu, Li-Gao Liu, Can-Ming Chen, Xiao Li, Zhou Xu, Xin Lu, Bo Zhou, Long-Wu Ye
Summary: [2,3]-Sigmatropic rearrangement reaction involving sulfonium ylide (Doyle-Kirmse reaction) generated from metal carbenes is a powerful method for the construction of C(sp(3))-S and C-C bonds. However, asymmetric versions using sulfonium ylides from metal carbenes as precursors have been rarely reported, and limited to diazo compounds. Here, we present a copper-catalyzed enantioselective Doyle-Kirmse reaction via azide-ynamide cyclization, providing chiral [1,4]thiazino[3,2-b]indoles with a quaternary carbon stereocenter in moderate to excellent yields and excellent enantioselectivities. Importantly, this protocol represents a unique catalytic asymmetric Doyle-Kirmse reaction through a non-diazo approach and an unprecedented asymmetric [2,3]-sigmatropic rearrangement via alpha-imino metal carbenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Organic
Claire Empel, Sripati Jana, Rene M. Koenigs
Summary: This review article summarizes the progress made on [1,2]-sigmatropic rearrangements using carbenes in the ylide formation step, highlighting the application of diazoalkanes as carbene precursors and the formation and application of various ylide species.
SYNTHESIS-STUTTGART
(2021)
Review
Chemistry, Physical
Kejia Wu, Minglong Cao, Qiang Zeng, Xuehui Li
Summary: Lignin, as a major component of woody biomass, is a natural organic polymer and the only abundant natural renewable resource with aromatic nucleus. Chemical catalysis induced depolymerization and photocatalysis and electrocatalysis are effective methods for lignin utilization. In this contribution, the radical and (photo)electron transfer induced reaction mechanisms of lignin depolymerization are discussed, along with the challenges and opportunities of photo(electro)catalysis in lignin valorization.
GREEN ENERGY & ENVIRONMENT
(2023)
Article
Chemistry, Multidisciplinary
Ricardo Meyrelles, Manuel Schupp, Boris Maryasin
Summary: A computational study reveals the mechanism of hydroxamic acid isomerization into para-aminophenols catalyzed by phenylselenyl bromide, providing insights into the reaction mechanism and explaining experimental observations. Joint theoretical and experimental studies also demonstrate the effectiveness of phenylsulfenyl bromide in mediating the reaction under the same conditions.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Yuya Okuyama, Mayu Kidena, Erina Kato, Sayaka Kawano, Koki Ishii, Kenta Maie, Kazuki Miura, Siro Simizu, Takaaki Sato, Noritaka Chida
Summary: A concise synthetic route to peracetylated all-nitrogenated sugars (ANSs) in seven steps from commercially available monosaccharides has been developed. The key to success is the use of sequential Overman rearrangement for ANS synthesis, which shows cytotoxicity against human cancer cell lines.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Biochemistry & Molecular Biology
Itaru Nakamura, Mai Tachibana, Riku Konta, Hiroki Tashiro, Masahiro Terada
Summary: Cu-catalyzed reactions of N-alkoxy-2-methylanilines and alcohols in the presence of IPrCuBr and AgSbF6 afford meta-aminophenol derivatives through a [1,3]-rearrangement and an oxa-Michael reaction.
Article
Chemistry, Organic
Dong-Dong Liang, Shen-Yi Guo, Shuo Tong, Mei-Xiang Wang
Summary: A practical synthetic method has been developed for polyfunctionalized biaryls based on one-pot nucleophilic aromatic substitution (SNAr) reaction and sigmatropic rearrangement reaction cascade. The resulting biaryls were used as invaluable building blocks in the synthesis of various organic compounds.
Article
Chemistry, Organic
Md Nirshad Alam, Soumya Ranjan Dash, Anirban Mukherjee, Satish Pandole, Udaya Kiran Marelli, Kumar Vanka, Pradip Maity
Summary: The thermal O-to-C [1,3]-rearrangement of alpha-hydroxy acid derived enol ethers was achieved under mild conditions, facilitated by the 2-aminothiophenol protection of carboxylic acids. Experimental and theoretical evidence was presented for dissociative radical pair formation, captodative stability via aminothiophenol, and a unique solvent effect. Aminothiophenol was deprotected from rearrangement products and after derivatization to useful synthons.
Article
Chemistry, Physical
Meng-Kai Liu, Jian Li, Quan-Song Li, Ze-Sheng Li
Summary: In this study, the photo-induced reaction mechanisms of phenylsulfinyl radical and its isomer phenoxathiyl radical were investigated using computational methods. The results revealed their different properties in the excited state and diverse reaction pathways after irradiation. The calculations were consistent with experimental observations and provided new insights into sulfinyl radicals and isomer oxathiyl radicals.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Review
Multidisciplinary Sciences
Hideki Yorimitsu, Gregory J. P. Perry
Summary: Biaryl synthesis plays a central role in chemical synthesis and offers numerous possibilities for various applications. In this study, a metal-free C-H/C-H coupling reaction was developed to synthesize intriguing aromatic molecules with unique structures. The researchers also expanded their methods based on a deeper understanding of the mechanistic steps involved in biaryl synthesis.
PROCEEDINGS OF THE JAPAN ACADEMY SERIES B-PHYSICAL AND BIOLOGICAL SCIENCES
(2022)
Article
Chemistry, Multidisciplinary
Xue Han, Li-Xin Shan, Jin-Xin Zhu, Chang-Sheng Zhang, Xiao-Ming Zhang, Fu-Min Zhang, Hong Wang, Yong-Qiang Tu, Ming Yang, Wen-Shuo Zhang
Summary: A novel copper-nitrene-catalyzed desymmetric oxaziridination reaction was reported, producing a synthetically challenging chiral bicyclic lactam. This enriches the asymmetric reactions involving copper-nitrene and provides an alternative strategy for addressing the challenges of catalytic asymmetric Schmidt reactions. This unique reaction could inspire further investigation into novel copper-nitrene-catalyzed asymmetric transformations and their reaction mechanisms.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Yu Tian, Aiji Wang, Yaqing Wei, Minghui Pei, Rongrong Cao, Zhenao Gu, Qi Yuan, Yiwen Hu, Jing Wang, Kunhui Liu, Dashan Shang, Jiebin Niu, Xiaoqiang An, Run Long, Jinxing Zhang
Summary: This study demonstrates a controllable water splitting reaction by constructing a hydroxyls-bonded surface on a ferroelectric material. The up-shift of band edge positions at this surface enhances the transfer of holes and electrons, leading to enhanced oxygen or hydrogen evolutions, respectively. Additionally, the introduction of ferroelectric super-domains with electric fields improves the separation of photogenerated carriers, resulting in a significant increase in photocurrent.
ADVANCED FUNCTIONAL MATERIALS
(2022)
Article
Chemistry, Physical
Junjie Dong, Chunhua Huang, Shaoshi Guo, Ye Xia, Yue Hou, Chunfan Yang, Xianwang Zhang, Jialong Jie, Ben-Zhan Zhu, Hongmei Su
Summary: By real-time observation of radical intermediates and product analysis, it is revealed that UVA excitation of 6-TG triggers direct covalent cross-linking with tryptophan, establishing a mechanistic framework for understanding mutagenic DPCs formation.
JOURNAL OF PHYSICAL CHEMISTRY B
(2022)
Article
Chemistry, Physical
Kangwei Wang, Guangwei Shao, Shaoqian Peng, Xiaoxiao You, Xingyu Chen, Jingwen Xu, Huaxi Huang, Huan Wang, Di Wu, Jianlong Xia
Summary: By mediating interchromophore coupling, symmetry-breaking charge separation can be achieved in a nonpolar solvent through the combination of bridge resonance and N-functionalization. Observation of the CT band confirms the enhanced electronic coupling. Transient absorption spectroscopy demonstrates the feasibility of photoinduced SB-CS in a nonpolar solvent.
JOURNAL OF PHYSICAL CHEMISTRY B
(2022)
Article
Chemistry, Physical
Min Tao, Yang Li, Quan Huang, Hongmei Zhao, Jingbo Lan, Yan Wan, Zhuoran Kuang, Andong Xia
Summary: This study demonstrates the feasibility of continuously modulating ESIPT dynamics in HPO derivatives by investigating electron population variations on proton donor and acceptor. An index Δpdif was proposed to evaluate the overall promotion effect on proton transfer, showing high reliability in interpreting the ESIPT tendency. This method has great potential in ESIPT molecular design with chemical substitution of electron-donating/withdrawing moieties.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Organic
Jie Wen, Lei Feng, Hongmei Zhao, Li Zheng, Pericles Stavropoulos, Lin Ai, Jiaxin Zhang
Summary: This study successfully established an unconventional enantiomeric discrimination method for hydantoin derivatives, representatives of five-membered N,N-heterocycles, and observed non-equivalent chemical shifts through H-1 NMR spectroscopy. Additionally, theoretical calculations were performed to understand the intermolecular interactions between chiral solvating agents and enantiomers.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Zheng Hu, Qian Zhou, Zeqing Jiao, Peixuan Qin, Fei Wang, Ye Xia, Tianfeng Zhang, Jialong Jie, Hongmei Su
Summary: This study demonstrates that phosphorothioate modified oligonucleotides undergo photoionization upon UV excitation, leading to the formation of hemi-bonded radicals. The presence of phosphorothioate moiety protects the remaining bases from ionization damage.
JOURNAL OF PHYSICAL CHEMISTRY B
(2022)
Article
Chemistry, Physical
Zeqing Jiao, Chunfan Yang, Qian Zhou, Zheng Hu, Jialong Jie, Xianwang Zhang, Hongmei Su
Summary: Triplex DNA structure has potential therapeutic application in inhibiting the expression of genes involved in cancer and other diseases. Coralyne, a DNA-targeting antitumor and antibiotic drug, shows remarkable binding propensity to triplex over canonical duplex, providing a prospective gene targeting strategy. By combining multiple spectroscopy techniques, the binding behaviors of coralyne with typical triplexes have been investigated, revealing the preferences and contributions of different binding modes. The strong pi-pi stacking of intercalated coralyne monomer with base-triplets plays an important role in stabilizing the triplex structure, offering mechanistic insights for the selective binding of coralyne to triplex DNA.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Qian Zhou, Tianfeng Zhang, Jialong Jie, Yue Hou, Zheng Hu, Zeqing Jiao, Hongmei Su
Summary: TiO2 has been found to exhibit photocatalytic properties similar to natural enzymes, showing its potential as a nanozyme to mimic photolyase in repairing DNA damage.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Physical
Shaoqian Peng, Guangwei Shao, Kangwei Wang, Xingyu Chen, Jingwen Xu, Huan Wang, Di Wu, Jianlong Xia
Summary: Investigated two antenna molecules with simplified structures to avoid complex exciton dynamics caused by conformational mobility. TP and TBP heterodimers with a PDI donor and TDI acting as an energy sink were studied. TP showed strong chromophore coupling, while TBP exhibited weak chromophore coupling. TP underwent ultrafast vibrational relaxation and electron transfer, while TBP demonstrated ultrafast excitation energy transfer with quenched charge transfer. This finding provides insight for designing novel small molecules capable of efficient energy transfer.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Biochemistry & Molecular Biology
Qian Zhou, Wenwen Guo, Zheng Hu, Shuyi Yan, Jialong Jie, Hongmei Su
Summary: Methylation significantly enhances the photoionization of DNA bases, with methylated purines exhibiting higher ionization yields and potentially acting as hotspots for DNA photoionization damage in living organisms.
PHOTOCHEMISTRY AND PHOTOBIOLOGY
(2023)
Article
Chemistry, Physical
Chunfan Yang, Fang Wang, Qian Zhou, Jialong Jie, Hongmei Su
Summary: This study investigates the fluorescence quenching dynamics of AMND in AP-containing DNA single/double strands and reveals that AMND only targets cytosine to form a pseudo-base pair. Subtle conformational variations induced by different flanking nucleobases are found to modulate efficiencies of electron transfer and fluorescence quenching, providing critical mechanistic insights for the design of fluorescent ligands for single-base recognition.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Wenshan Xiao, Mingwei Wu, Huan Wang, Qiu He, Yan Zhao
Summary: This article proposes a method for obtaining ideal artificial solid-electrolyte interface (SEI) materials for lithium metal anodes (LMAs) through chemical stability assessments, electronic conductivity measurements, and accurate predictions of key parameters. The method was demonstrated by finding optimal SEI materials from 76 binary selenides for LMAs.
JOURNAL OF MATERIALS CHEMISTRY A
(2022)
Article
Chemistry, Multidisciplinary
Wei Yang, Chen Wang, Kunhui Liu, Chao Liu, Jianzhuang Jiang
Summary: A pair of chiral metallic porphyrin cages have been synthesized and their structure and photophysical properties have been studied. These cages exhibit superior photosensitive performance compared to the monomeric compound in solution.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Physics, Atomic, Molecular & Chemical
Chen Wang, Ming-chen Xiong, Xuan Zhao, Kun-hui Liu
Summary: This study directly investigated the reaction rate constant of atenolol with singlet oxygen by observing the decay of O-1(2) phosphorescence, revealing rate constants of 7.0x10(5), 8.0x10(6) and 8.4x10(5) (mol/L)(-1)& BULL;s(-1) in D2O, acetonitrile, and EtOH respectively. It was also found that solvents with strong polarity and weak hydrogen donating ability are suitable for achieving high rate constant values.
CHINESE JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Lixue Xia, Huan Wang, Yan Zhao
Summary: This study presents a new approach in designing photocatalysts with higher electron conductivity and longer wavelength absorption. The newly designed graphitic carbon nitride g-C9N10 shows enhanced photoactivity, particularly in nitrogen reduction reactions. With low overpotential for reducing N-2 to NH3 and efficient suppression of the competitive hydrogen evolution reaction, B@g-C9N10 exhibits spontaneous NRR capability under visible/infrared light irradiation.
JOURNAL OF MATERIALS CHEMISTRY A
(2021)