Article
Chemistry, Multidisciplinary
Yongsuk Jung, Seok Yeol Yoo, Yonghoon Jin, Jaehyun You, Seungcheol Han, Jeongwoo Yu, Yoonsu Park, Seung Hwan Cho
Summary: In this study, a highly selective allyl-allyl coupling reaction between branched allyl alcohols and alpha-silyl-substituted allylboronate esters was reported, catalyzed by a chiral iridium complex. By permuting the chiral iridium catalysts and the substrates, all four stereoisomers bearing two consecutive chiral centers were efficiently obtained. Mechanistic studies revealed the origins of the diastereo- and chemoselectivities, and additional synthetic modifications for preparing enantioenriched compounds containing contiguous chiral centers were also included.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Andrey S. Kozlov, Oleg I. Afanasyev, Denis Chusov
Summary: Borrowing hydrogen amination is a common method for the formation of C-N bonds, which can be carried out without transition metal catalysts at low temperatures. Through experimental investigation, optimal conditions can be predicted and the need for transition metal catalysts can be determined.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Physical
Kuhali Das, Koushik Sarkar, Biplab Maji
Summary: This article presents a method for selective formal anti-Markovnikov hydroamination of allyl alcohols, enabling the synthesis of valuable gamma-amino alcohol building blocks. Catalyzed by a phosphine-free Earth's abundant manganese(I) complex, a wide range of hydroamination reactions were successfully conducted with excellent functional group tolerance. The mechanistic studies highlighted the importance of metal-ligand bifunctionality and ligand backbone hemilability for the success of this catalysis.
Article
Chemistry, Multidisciplinary
Eliezer Ortiz, Madeline M. Evarts, Zachary H. Strong, Jonathan Z. Shezaf, Michael J. Krische
Summary: The first metal-catalyzed oxidative alkynylations of primary alcohols or aldehydes to form alpha,beta-acetylenic ketones (ynones) are reported. Deuterium labelling studies support a novel reaction mechanism in which alkyne hydroruthenation induces the formation of a transient vinylruthenium complex, which then deprotonates the terminal alkyne to produce an active alkynylruthenium nucleophile.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Lipeng Qiao, Xiaoyang Fu, Yafeng Si, Xiaolan Chen, Lingbo Qu, Bing Yu
Summary: A photocatalytic strategy using tetrabutylammonium decatungstate (TBADT) as a hydrogen atom transfer (HAT) photocatalyst and aldehydes as radical precursors was developed for the controllable aroylation or diaroylation of allyl sulfones. By adjusting the substrate ratio, the selectivity of the reaction could be easily tuned, resulting in the installation of various aroyl groups on allyl sulfones, and the formation of beta,gamma-unsaturated ketones and 1,5-diketones with moderate to excellent yields. This methodology offers mild conditions, high step economy, no external additive, readily available resources, and broad substrate scope.
Article
Chemistry, Multidisciplinary
Kathleen M. Morrison, Charles S. Yeung, Mark Stradiotto
Summary: A systematic evaluation of competitive bisphosphine/Ni-catalyzed C-N versus C-O cross-couplings involving model compounds enabled the development of selective O- and N-arylation of amino alcohols with (hetero)aryl chloride electrophiles, without the need for protection group chemistry. The use of the CyPAd-DalPhos pre-catalyst C2 allowed for challenging O-arylation in amino alcohols with branched alkylamine groups, while selective N-arylation was observed in substrates with less hindered linear alkylamine and aniline groups. The reaction scope in (hetero)aryl chloride was broad, and the transformations could be conducted using benchtop handling of materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Materials Science, Ceramics
O. H. Borges, F. G. Coury, D. N. F. Muche, V. C. Pandolfelli
Summary: In this study, multiple electron-microscope-based techniques were applied to assess the microstructural features of electrofused magnesia-chromite aggregate (EMCA). The results showed that the aggregates were comprised of a periclase matrix with embedded spinel precipitates, which induced microcracking due to thermal expansion mismatch. By designing compositionally complex ceramics, eco-friendly alternatives to EMCA were found and successfully produced. This study highlights the potential of the design approach in supporting the development of novel raw materials.
JOURNAL OF THE EUROPEAN CERAMIC SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Chao Gao, Qingqing Xuan, Qiuling Song
Summary: Efficient catalytic system using H3N·BH3 as the hydrogen source in CuSO4 solution was developed for the reduction of N-heteroaromatics, showing excellent chemoselectivity and broad functional group tolerance. Various challenging substrates were smoothly reduced, possibly via the generation of [Cu-H] intermediate in the reaction.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
De-Hai Liu, Kyogo Nagashima, Hui Liang, Xue-Lin Yue, Yun-Peng Chu, Shuming Chen, Jiajia Ma
Summary: This study introduces a highly chemoselective protocol for the reduction of quinoline and isoquinoline through selective energy transfer catalysis. The protocol bypasses the traditional metric of reduction reaction and relies on the triplet energies of chemical moieties and the kinetic barriers of energy and hydrogen atom transfer events. It retains many reducing labile functional groups that were previously incompatible.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Charlotte E. Coomber, Louis J. Diorazio
Summary: The iridium catalysed N-alkylation of alpha-amino esters and amides using alcohols through hydrogen borrowing method has been developed. This protocol is applicable to both free base and hydrochloride salts of the amines and produces water as the sole by-product. This transformation provides an easy access to chiral N-alkyl amines from readily available starting materials in a simple one-step reaction.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Cody Loy, Jana M. Holthoff, Robert Weiss, Stefan M. Huber, Sergiy V. Rosokha
Summary: Halogen-bonded complexes between halide anions and a cyclopropenylium-based anionic XB donor were characterized in solution for the first time, showing that halogen bonding is strong enough to overcome electrostatic repulsion. The formation constants of these complexes are comparable to others, but their UV-Vis spectra are determined by the electronic excitations within the XB donor.
Article
Chemistry, Organic
Yongsuk Jung, Seung Hwan Cho
Summary: Here, we developed a transition-metal-free electrophilic fluorodesilylation reaction of α-silyl-substituted allylboronate esters. The reaction showed chemo-, regio-, and stereoselectivity, and resulted in the formation of (E)-boryl-substituted allyl fluorides through a selective coupling with Selectfluor. The obtained (E)-boryl-substituted allyl fluorides were further modified to afford allyl or alkyl fluoride derivatives.
Article
Chemistry, Physical
Marvin C. Schmidt, Carsten Schroeder, Philipp A. Haugg, Ann-Katrin Baumann, Jan Smyczek, Swetlana Schauermann
Summary: We conducted a mechanistic study on the interaction between allyl cyanide (AC) and Pd(111), and observed the formation of different types of self-organized 2D layers at different temperatures. By using scanning tunneling microscopy and infrared reflection absorption spectroscopy, we obtained complementary information on the distribution and chemical structure of AC molecules in the self-organized 2D layers.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Physical
Michael T. Bender, Robert E. Warburton, Sharon Hammes-Schiffer, Kyoung-Shin Choi
Summary: This study investigated the key factors and steps affecting the kinetics of two oxidation pathways by examining the pH and the concentration of aliphatic and aromatic alcohols and aldehydes. Through experiments and kinetic isotope effect studies, the researchers obtained a comprehensive mechanistic understanding of the two pathways. The ability of alcohols and aldehydes to outcompete OH- for adsorption on Ni4+ sites was proposed as a key predictor of which oxidation pathway will be favored.
Article
Environmental Sciences
Zhimin Mao, Yanru Huang, Bingqian Li, Kazutoshi Tomoya, Hideyuki Shinmori, Xuhui Zeng, Zhifeng Gu, Jian Yao
Summary: The study found that hydrogen sulfide (H2S) can effectively detoxify acrolein (ACR) toxicity, and increasing H2S levels can enhance cell resistance to ACR, while inhibiting H2S makes cells more sensitive. In animal experiments, inhibiting endogenous H2S increased sensitivity to ACR toxicity. Further analysis showed that H2S directly reacted with ACR, promoting ACR clearance and preventing protein carbonylation initiated by ACR.
ECOTOXICOLOGY AND ENVIRONMENTAL SAFETY
(2022)
Article
Chemistry, Physical
Marek Glinski, Urszula Ulkowska
APPLIED CATALYSIS A-GENERAL
(2018)
Article
Chemistry, Multidisciplinary
Ewa Iwanek (nee Wilczkowska), Marek Glinski
JOURNAL OF CHEMICAL EDUCATION
(2018)
Article
Chemistry, Physical
Marek Marczewski, Yuliya Kavalchuk, Urszula Ulkowska, Marek Glinski, Osazuwa Osawaru
REACTION KINETICS MECHANISMS AND CATALYSIS
(2019)
Article
Chemistry, Physical
Marek Marczewski, Monika Aleksandrowicz, Ewelina Brzezinska, Maja Podlewska, Mateusz Rychlik, Sandra Zmuda, Urszula Ulkowska, Marek Glinski, Osazuwa Osawaru
REACTION KINETICS MECHANISMS AND CATALYSIS
(2019)
Article
Chemistry, Physical
Ewa M. Iwanek (nee Wilczkowska), Leonarda F. Liotta, Shazam Williams, Linjie Hu, Krishelle Calilung, Giuseppe Pantaleo, Zbigniew Kaszkur, Donald W. Kirk, Marek Glinski
Article
Chemistry, Multidisciplinary
Urszula Ulkowska, Marek Glinski
Summary: The experiment course involves undergraduate students synthesizing 20% MnO2/Al2O3 catalyst and using it in the propionic acid ketonization reaction. They conduct the reaction in a flow system with a solid catalyst bed at temperatures ranging from 573 to 673 K. In addition, students perform thermodynamic calculations to estimate Gibbs free energy, equilibrium constant, and substrate conversion.
JOURNAL OF FLOW CHEMISTRY
(2021)
Article
Chemistry, Physical
Marek Glinski, Anna Markowska, Laura Wronska, Anna Jerzak, Magdalena Tarkowska
Summary: MgO has been proven to catalyze hydrogen transfer from 2-octanol to benzophenone to form benzhydrol, which is an important intermediate in the pharmaceutical industry. The study investigated the effects of hydrogen donor structure, reaction conditions, and catalyst amount on the reaction, determining optimal conditions for selective synthesis of alcohols and also studying side reactions.
Article
Materials Science, Ceramics
Radoslaw Zurowski, Justyna Zygmuntowicz, Justyna Tomaszewska, Urszula Ulkowska, Paulina Piotrkiewicz, Marcin Wachowski, Ireneusz Szachogluchowicz, Michal Kukielski
Summary: The paper introduces a centrifugal slip casting method for forming ceramic sleeves with good shape representation, eliminating material losses. These sleeves can be used as system components to transport aggressive substances. Tests confirm the formation of expected gradient structures, resulting in improved strength.
CERAMICS INTERNATIONAL
(2022)
Article
Chemistry, Physical
Marek Glinski, Ewa M. Iwanek (nee Wilczkowska), Urszula Ulkowska, Agnieszka Czajka, Zbigniew Kaszkur
Summary: The research first aimed to synthesize a pure Upsalite, which would act as a precursor for high-surface, amorphous magnesium oxide. It was found that the type of alcohol reactant used had the most significant effect on the reaction yield. The optimized synthesis conditions were then used to obtain MgO which showed selective catalytic activity in transfer hydrogenation reactions.
Article
Chemistry, Physical
Ewa M. Iwanek (nee Wilczkowska), Marek Glinski, Aleksandra Siwiec, Sylwia Siennicka, Magdalena Zybert, Zbigniew Kaszkur
Summary: In the liquid phase catalytic transfer hydrogenation of acetophenone with 2-pentanol, larger gold particles (over 30 nm in diameter) exhibited higher catalytic activity compared to smaller particles (4 nm in size). This is contrary to what is observed with supported monometallic silver catalysts.
Article
Chemistry, Physical
Marek Glinski, Agnieszka Czajka, Urszula Ulkowska, Ewa M. Iwanek (nee Wilczkowska), Dariusz Lomot, Zbigniew Kaszkur
Summary: This study investigates the synthesis of Mg(OH)(2) using magnesium nitrate, chloride, or sulphate, finding that the counter ion strongly influences purity and specific surface area. Factors such as calcination temperature and choice of precipitating agent also play a role in the properties of the obtained MgO.