Article
Chemistry, Physical
Matthew E. Grundy, Lia Sotorrios, Milan Kumar Bisai, Kang Yuan, Stuart A. Macgregor, Michael J. Ingleson
Summary: [(NacNac)Zn(DMT)][B(C6F5)4], 1, was synthesized and demonstrated as an efficient catalyst for the C-H borylation of (hetero)arenes using catecholborane. Computational studies revealed a plausible mechanism involving displacement of DMT by CatBH and subsequent steps including dehydrocoupling and displacement of CatBAr. The research also provided insight into a possible decomposition pathway of the catalyst involving boron to zinc hydride transfer.
Article
Chemistry, Physical
Matthew E. Grundy, Lia Sotorrios, Milan Kumar Bisai, Kang Yuan, Stuart A. Macgregor, Michael J. Ingleson
Summary: This article reports the synthesis of (NacNac)Zn(DMT) complex via two different routes and its use as a catalyst for C-H borylation. Computational studies elucidated the reaction mechanism and revealed the influence of the electronic and steric parameters of the base on the catalyst's performance.
Article
Chemistry, Physical
Francisco de Azambuja, Jille Lenie, Tatjana N. Parac-Vogt
Summary: Inorganic clusters, specifically polyoxometalates (POMs), can serve as effective ligands for Hf(IV) Lewis acid metals in homogeneous metal catalysis. The interplay between the dielectric constant of the medium and the ligand structure is crucial for optimizing catalytic activity and promoting efficient amide bond formation. Changes in the dielectric constant can significantly impact the performance of the catalyst, highlighting the importance of understanding the relationship between medium properties and catalyst reactivity.
Article
Chemistry, Multidisciplinary
Xiuxiu Yang, Jennifer Kuziola, Vanessa A. Beland, Julia Busch, Markus Leutzsch, Jordi Bures, Josep Cornella
Summary: This article reports the use of a cationic version of Akiba's Bi-III complex as a catalyst for the reduction of amides to amines using silane as a hydride donor. The catalytic system exhibits low catalyst loadings and mild conditions, leading to the synthesis of secondary and tertiary aryl- and alkylamines. The system is tolerant to various functional groups. Kinetic studies reveal the presence of a product inhibition in the reaction mechanism, consistent with experimental reaction profiles.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Yakun Wang, Shuaifei Wang, Yufeng Wu, Ting Zhao, Jie Liu, Junlin Zheng, Lin Wang, Jieli Lv, Tao Zhang
Summary: We have developed a highly efficient enantioselective fluorination reaction of 4-substituted pyrazolones using amide-based Cinchona alkaloids catalysts. The reaction affords tetrasubstituted fluorine-attached chiral center products in high yields (up to 99%) and excellent enantioselectivities (up to 98% ee). Our method features low catalyst loading, short reaction times, and wide substrate scope. Furthermore, the reaction can be carried out under sustainable conditions for 10 cycles, and the optically pure product (>99.5% ee) can be easily obtained on a multigram scale through simple extraction and recrystallization. Controlled experiments and DFT studies revealed that the multiple hydrogen bonding interactions and steric hindrance contribute to the high enantioselectivity and reactivity. This transformation provides a practical method for the preparation of chiral fluorine-containing compounds with a simple operational protocol and low catalyst loading.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Haonan Zhou, Peihsuan Chuang, Leyan Xu, Qi Wu
Summary: Enzymatic reduction of diphenylmethanimine derivatives with steric hindrance was rarely reported. In this study, imine reductase (IRED) from Nocardia cyriacigeorgica was engineered with focused rational iterative site-specific mutagenesis (FRISM) strategy, resulting in two highly enantioselective IRED variants that could efficiently reduce N-cyclopropylmethyl-1-aryl-1-phenylmethylimines to bulky amine products with high yields and ee values (>99%). This work provides an effective method for constructing important pharmaceutical intermediates.
Review
Chemistry, Multidisciplinary
Minghao Feng, Haoqi Zhang, Nuno Maulide
Summary: Compared to ketones and carboxylic esters, amides have traditionally been considered as less reactive members of the carbonyl family. However, recent research has shown that selective activation of amides under mild conditions is possible. This Minireview highlights the latest advances in this field, showcasing new strategies and breakthroughs in amide activation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Jeffrey M. Lipshultz, Alexander T. Radosevich
Summary: This study reports an organophosphorus catalyzed method for the three-component condensation to generate 2-amidopyridines via serial dehydration, enabling new possibilities for the efficient and modular preparation of medicinal targets. The phosphetane catalyst can drive both amide synthesis and functionalization in an auto-tandem catalytic cascade, showing chemoselectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Meng Li, Dong-Hui Wang
Summary: A copper-catalyzed method for synthesizing ortho-aminoazulenols by reacting 2-azulenols with O-benzoylhydroxylamines has been reported, with a wide range of functional groups on amines being compatible. Further synthetic elaboration using 3-amino-2-azulenols as starting materials has been demonstrated.
Article
Chemistry, Multidisciplinary
Jordan Berreur, Alberto Diez-Varga, Augustin Manel, Frederic R. Leroux, Armen Panossian
Summary: The direct oxidative monofluorination of sulfoxides can be achieved using a strongly oxidizing, powerful electrophilic fluorination reagent [FXe][OTf], without the need for a chloride promoter. This method allows the synthesis of highly desirable strongly Lewis acidic fluorosulfoxonium cations, which were previously difficult to access using the XeF2/NEt4Cl system. Experimental and theoretical studies were conducted to evaluate the Lewis acidities of the prepared sulfur(VI) cations, and early insights into the mechanism of these fluorination reactions were obtained through preliminary studies with chiral sulfoxides.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Chen-Yu Huo, Tian-Lu Zheng, Wei-Hao Dai, Zi-Hao Zhang, Jin-Da Wang, Dao-Yong Zhu, Shao-Hua Wang, Xiao-Ming Zhang, Xue-Tao Xu
Summary: A novel polyene cyclization method utilizing the allene group as the initiator has been successfully developed. This efficient strategy enables the construction of an abietane-type tricyclic skeleton with a functionalizable C2-C3 double bond, exhibiting a wide substrate scope and excellent stereoselectivities. The potential utility of this approach has been demonstrated through the total synthesis of seven abietane-type diterpenoids, including the first synthesis of (+/-)-2,3-dihydroxyferruginol and (+/-)-2,3-dihydroxy-15,16-dinor-ent-pimar-8,11,13-triene.
Article
Biochemistry & Molecular Biology
Christopher H. Switzer, Sebastian Guttzeit, Thomas R. Eykyn, Philip Eaton
Summary: The study demonstrates that cysteine trisulfide induces cellular stress response, inhibits cellular metabolism and proliferation, and protects cells from ER stress through the generation of cysteine persulfide.
Article
Chemistry, Multidisciplinary
Jacqueline Ramler, Felipe Fantuzzi, Felix Geist, Anna Hanft, Holger Braunschweig, Bernd Engels, Crispin Lichtenberg
Summary: The isolated and characterized dimethylbismuth cation reacts with BiMe3 to form an unprecedented Bi -> Bi donor-acceptor interaction, which is a fundamental type of reaction in organometallic chemistry. This work provides insights into the exchange of methyl groups between different metal atoms, shedding light on novel bonding scenarios and reactivity in organometallic compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Multidisciplinary Sciences
Weijin Wang, Xinyao Li, Xiaoxue Yang, Lingsheng Ai, Zhiwen Gong, Ning Jiao, Song Song
Summary: TEMPO and its derivatives are active catalysts for electrophilic halogenation of olefins, alkynes, and aromatics, under mild reaction conditions and with good functional group tolerance. The high catalytic ability is attributed to a synergistic activation model of electrophilic halogenating reagents. Organohalides are widely used as synthetic precursors and target products, and effective catalysts are needed to activate commercially available haleniums for various halogenation reactions.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Weiwei Jin, Shouyun Yu
Summary: The photoinduced and palladium-catalyzed remote desaturation of O-acyl hydroxamides to unsaturated amides under mild conditions has been achieved efficiently and selectively. This method features good site-selectivity, is terminal oxidant-free, and produces moderate to excellent yields for a variety of unsaturated amides, enabling late-stage desaturation of complex and biologically important molecules.
Article
Chemistry, Organic
Yao Shi, Jonathan Wong, Zhihai Ke, Ying-Yeung Yeung
JOURNAL OF ORGANIC CHEMISTRY
(2019)
Article
Chemistry, Organic
Jonathan Wong, Zhihai Ke, Ying-Yeung Yeung
TETRAHEDRON LETTERS
(2020)
Article
Chemistry, Applied
Vincent Ming-Yau Leung, Matthew H. Gieuw, Zhihai Ke, Ying-Yeung Yeung
ADVANCED SYNTHESIS & CATALYSIS
(2020)
Article
Chemistry, Organic
Zhihai Ke, Ying-Pong Lam, Kin-San Chan, Ying-Yeung Yeung
Article
Chemistry, Organic
Liangkun Pan, Zhihai Ke, Ying-Yeung Yeung
Summary: In this study, a catalytic vicinal dioxygenation of olefins with hypervalent iodine reagents using Lewis bases as catalysts was reported. The conditions are mild and compatible with various functional groups.
Article
Chemistry, Physical
Xinxin He, Xinyan Wang, Ying-Lung Steve Tse, Zhihai Ke, Ying-Yeung Yeung
Summary: Bidentate Lewis acid catalysts derived from selenonium dicationic centers have been developed for various transformations with good yields and selectivity. These catalysts exhibit stronger Lewis acidity compared to monoselenonium systems due to the synergistic effect of the two cationic selenonium centers, and are not inhibited by strong bases or moisture.
Article
Chemistry, Multidisciplinary
Qingyu Zhang, Yongyuan Xu, Xiaochen Liang, Zhihai Ke
Summary: Efficient amphiphilic indole-based phase-transfer organocatalysts were developed for environmentally benign bromination reactions in water. The method allowed for greener and more sustainable bromination reactions, producing the corresponding bromides in good yields. Some pure products could be obtained without column chromatography.
Article
Chemistry, Multidisciplinary
Yanjie Wu, Zhihai Ke
Summary: Cu-doped ZIF-8 membranes were prepared for the catalytic wet peroxide oxidation of phenol. The membrane doped with 5% copper exhibited the best catalytic performance and showed good reusability and stability. The effects of reaction temperature, feed flow rate, and catalyst bed height were investigated to obtain the optimal reaction conditions. The material has economical characteristics such as short reaction time, low metal loading, easy recycling, and good stability.
MATERIALS TODAY CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Liangkun Pan, Long Zheng, Ye Chen, Zhihai Ke, Ying-Yeung Yeung
Summary: A mechanochemical method using hypervalent iodine reagents has been developed for the functionalization of olefins, enabling the synthesis of 1,3-dioxygenated compounds. Under similar reaction conditions with the addition of molecular iodine, 1,4-iodoalcohols can also be synthesized. These valuable products are difficult to achieve using traditional solution-phase methods. Mechanistic study suggests that the hypervalent iodine reagent may dimerize at the solid state and trigger the 1,3- and 1,4-difunctionalization reactions in an intermolecular cascade manner.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Liangkun Pan, Ka-Mei Lee, Yung-Yin Chan, Zhihai Ke, Ying-Yeung Yeung
Summary: Non-symmetrical bromoiodanes are useful for bromination reactions, and specific protocols, like DIB/BBr3 method, can be used for various bromination reactions such as electrophilic bromination of arenes, carbonyl C-H monobromination, bromolactonization, bromocarbocyclization, intermolecular bromoetherification of olefin, and light-triggered C(sp3)-H bromination.
Article
Nanoscience & Nanotechnology
Yanjie Wu, Yucheng Yang, Zhihai Ke
Summary: Graphdiyne (GDY) with a three-dimensional network structure was synthesized on a copper foam (CF) via an in situ Glaser-Hay coupling reaction. A metal-organic framework/GDY composite membrane was designed and synthesized for the first time. The catalytic activities of HKUST-1/GDY/CF membrane in wet peroxide oxidation of phenol, oxidation of benzyl alcohol, and ring opening of epoxide were studied.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Yinglin Zheng, Zhihai Ke
Summary: This study demonstrates the birth of visible and selective click covalent assembly, which amplifies specific click chemistry reactions. This assembly method has important applications at the macroscale, providing more possibilities for material design.
Article
Chemistry, Multidisciplinary
Liangkun Pan, Ka-Mei Lee, Zhihai Ke, Ying-Yeung Yeung
Summary: Metal-free direct C-H functionalization reactions are a promising approach to convert hydrocarbon feedstock into value-added molecules. Diacetoxyl iodobenzene (DIB) is a frequently used non-metal oxidant in C-H functionalization, but it has relatively low reactivity and often requires an acid promoter for satisfactory performance.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Organic
Chi-Hang Fan, Tianyue Xu, Zhihai Ke, Ying-Yeung Yeung
Summary: In this study, Hantzsch pyridine was used as a promoter to activate Hantzsch ester for the generation of hydrogen peroxy radicals, which enables the ipso-hydroxylation of arylboronic acids to form phenols. The reaction conditions were mild and highly compatible with various functional groups.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Matthew H. Gieuw, Shuming Chen, Zhihai Ke, K. N. Houk, Ying-Yeung Yeung
