Article
Chemistry, Multidisciplinary
Sheng-Qi Qiu, Yu Chen, Xiang-Jun Peng, Shi-Jiang He, Jun Kee Cheng, Yong-Bin Wang, Shao-Hua Xiang, Jun Song, Peiyuan Yu, Junmin Zhang, Bin Tan
Summary: In this study, we achieved the arene-alkene Suzuki-Miyaura coupling reaction between hindered aryl halides and vinyl boronates by designing appropriate ligands and reaction parameters. The axially chiral acyclic aryl-alkenes obtained exhibited remarkable efficiency, enantioselectivity, and E/Z selectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Chaoyan Ma, Can Li, Jiahui Bai, Junzhe Xiao, Yizhan Zhai, Yinlong Guo, Shengming Ma
Summary: In this study, a rhodium-catalyzed C-H functionalization-based intermolecular allylation of indoles with trisubstituted allenes has been developed. The synthetic process demonstrates excellent regioselectivity, Z-selectivity, high efficiency of chirality transfer, and a wide tolerance of reactive functional groups under mild conditions. Late-stage modification on complex bioactive or drug molecules has been achieved, along with various synthetic transformations. A reaction mechanism has been proposed based on mechanistic experiments and SAESI-MS studies.
Article
Chemistry, Organic
Yanxin Jiang, Kwai Wun Cheng, Haoyang Zhang, Zhiping Yang, Jun Wang
Summary: A new palladium-catalyzed asymmetric Suzuki-Miyaura coupling is demonstrated using a unique monophosphine ligand, Azaphos. This method offers a novel ligand framework for the synthesis of axially chiral compounds via asymmetric Suzuki-Miyaura coupling reactions.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Physical
Julia E. Borowski, Samuel H. Newman-Stonebraker, Abigail G. Doyle
Summary: A comparison study of mono- and bisphosphine ligands in Ni-catalyzed Suzuki-Miyaura cross-coupling reactions revealed that monophosphines exhibit higher reactivity, particularly with electronically deactivated and sterically hindered substrates. Mechanistic experiments showed that monoligated (P1Ni) species accelerate the organometallic steps of the catalytic cycle, while bisligated (P2Ni) species prevent off-cycle reactions and catalyst poisoning by heterocyclic motifs. These findings provide guidelines for ligand selection against challenging substrates and future ligand design tailored to the mechanistic demands of Ni-catalyzed cross-coupling reactions.
Article
Chemistry, Physical
Da Xu, Yu Chang, Yidong Liu, Wenling Qin, Hailong Yan
Summary: This study achieved the enantioselective construction of stable VQM intermediates through organocatalyzed bromination, and revealed the mechanistic details of the two sequential events in VQM-involved reactions. The high potential of VQM as axially chiral synthetic reagents in organic chemistry was demonstrated.
Article
Chemistry, Organic
Hirokazu Seto, Takumi Tono, Akiko Nagaoka, Mai Yamamoto, Yumiko Hirohashi, Hiroyuki Shinto
Summary: Poly(vinylbiphenyl)s bearing glycoside ligands at the side chains were prepared using the Suzuku coupling reaction. The effects of glycoside reactant concentration, halide species, glycoside species, and catalyst species on the incorporation of glycoside ligand into the polymer were investigated. The obtained glycopolymers exhibited specific binding to proteins corresponding to the glycoside ligands and showed fluorescent properties due to the biphenyl spacers formed during the Suzuki coupling reaction.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Multidisciplinary Sciences
Chang You, Mingying Shi, Xueling Mi, Sanzhong Luo
Summary: In this study, a synergistic chiral primary amine/Pd catalyst was used to enable the utilization of 1,3-enynes as atom-economic and achiral allene precursors. The synergistic catalysis allowed the construction of all-carbon quaternary centers-tethered allenes with non-adjacent 1,3-axial central stereogenic centers in high diastereo- and enantio-selectivity. By switching the configurations of ligands and aminocatalysts, diastereodivergence was achieved and any of the four diastereoisomers could be accessed in high selectivity. Enantioselective alpha-allylic allenylation of carbonyls is a straightforward approach to access chiral allenes that are important in synthesis and as bio-active products.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Gaoyuan Zhao, Wang Yao, Ilia Kevlishvili, Jaclyn N. Mauro, Peng Liu, Ming-Yu Ngai
Summary: Nickel catalysis offers exciting opportunities for addressing challenges in organic synthesis. A novel nickel-catalyzed radical migratory cross-coupling reaction was reported for the direct preparation of 2-aryl-2-deoxyglycosides from readily available 1-bromosugars and arylboronic acids. This reaction shows a broad substrate scope, high tolerance to functional groups, and efficient synthesis of valuable carbohydrate mimics and building blocks.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Materials Science, Multidisciplinary
Kewang Zheng, Fang Yang, Zhihan Huang, Yifei Zhan, Zufeng Xiao, Wei Li, Wei Wang, Caiqin Qin
Summary: This paper discusses the preparation of chitosan-polyvinyl alcohol thin film solid loaded palladium catalytic materials by blending and modifying chitosan with polyvinyl alcohol. The catalytic material shows good substrate tolerance, catalytic activity, and recovery performance when applied in the Suzuki coupling reaction.
JOURNAL OF MATERIALS RESEARCH AND TECHNOLOGY-JMR&T
(2022)
Article
Chemistry, Multidisciplinary
Sandra Miguez-Lago, Bettina D. Gliemann, Milan Kivala, Maria Magdalena Cid
Summary: In this paper, scientists reported the synthesis and characterization of a chiral shape-persistent molecular cage based on the combination of enantiopure diethynylallenes and electron-rich bridged triarylamines. The experimental results revealed that this molecular cage has good chiral recognition ability in solution.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
David Augros, Corinne Comoy, Yves Fort, Frederic R. Leroux, Armen Panossian
Summary: This study investigates the challenging atropo-enantioselective coupling of in-situ generated arynes and aryllithiums in the presence of a chiral ligand of lithium for the first time. It demonstrates the feasibility of this concept, by affording enantioenriched axially chiral biaryls even in the case of products showing a high degree of steric congestion around the newly created aryl-aryl bond.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Multidisciplinary Sciences
Lara E. Zetzsche, Jessica A. Yazarians, Suman Chakrabarty, Meagan E. Hinze, Lauren A. M. Murray, April L. Lukowski, Leo A. Joyce, Alison R. H. Narayan
Summary: This study demonstrates the use of cytochrome P450 enzymes for biocatalytic cross-coupling reactions, enabling the formation of sterically hindered biaryl bonds through oxidative C-C bond formation. By engineering the substrate and atroposelectivity of the P450 enzyme, a highly efficient and selective process has been developed.
Article
Chemistry, Organic
Raphael K. Klake, Joshua D. Sieber
Summary: In this study, a Cu-catalyzed aminoallylation of aldehyde electrophiles through reductive coupling was developed by avoiding the competitive reduction of the aldehyde electrophile by a CuH catalyst. This process resulted in a highly diastereo- and enantioselective synthesis of chiral 1,2-aminoalcohols with secondary alcohol substitution. Cleavage of the N substituents on the reaction products allowed access to the other diastereomer of the aminoalcohol, which was studied in the context of a synthesis of eligulstat.
Article
Chemistry, Physical
Craig S. S. Day, Angel Renteria-Gomez, Stephanie J. J. Ton, Achyut Ranjan Gogoi, Osvaldo Gutierrez, Ruben Martin
Summary: Polypyridine-ligated nickel complexes are widely used as privileged catalysts in cross-coupling reactions due to their ability to shuttle between different oxidation states. However, the mechanistic understanding of these reactions is limited. In this study, the reactivity of pseudohalide- and halide-ligated Ni(II) complexes with polypyridine ligands in electron-transfer reactions is investigated. Electrochemical techniques and quantum mechanical calculations support the observations regarding the different behaviors of Ni(II) halide and pseudohalide complexes. Reactivation of catalytically inactive Ni(II) pseudohalide complexes in the presence of exogenous salts is also demonstrated. Overall, this study provides insights into the overlooked steps in Ni-catalyzed cross-coupling reactions and offers guidance for future reaction design.
Article
Biochemistry & Molecular Biology
Martina Hurtova, David Biedermann, Zuzana Osifova, Josef Cvacka, Katerina Valentova, Vladimir Kren
Summary: In this study, we utilized the Suzuki-Miyaura cross-coupling reaction to synthesize a library of flavonoid derivatives for biological activity assays. We explored the reactivity of halogenated flavonoids with aryl boronates and boronyl flavonoids. This method enabled the preparation of various flavonoid derivatives substituted at C-8, and was successfully applied to the synthesis of natural compounds and rare C-8 hydroxyflavonoids.
