Article
Chemistry, Inorganic & Nuclear
Alexandra B. Grimm, Kai Wang, Arnold L. Rheingold, Curtis E. Moore, Denes Szieberth, Laszlo Nyulaszi, John D. Protasiewicz
Summary: The palladium Suzuki-Miyaura coupling reactions of p-tolylboronic acid and 2-(BrC6H4)-1,3-benzoxaphosphole did not result in the anticipated product, indicating the formation of labile metal complexes with unusual bridging mu(2)-P-BOP bonding modes. Computational studies show that these dimeric complexes can dissociate easily, even when the P=C double bonds are protected by coordination to tungsten pentacarbonyl. Furthermore, under similar conditions, the Ar-BOP units resist CC coupling and instead yield unusual products with CsOH adding across the P=C bonds.
Review
Chemistry, Multidisciplinary
Martin Tomanik, Ian Tingyung Hsu, Seth B. Herzon
Summary: Fragment coupling reactions that form carbon-carbon bonds are important transformations in synthetic design. In recent years, there has been an increase in fragment couplings proceeding via carbanionic and open-shell intermediates. These reactions provide predictability and reliability, while also offering valuable lessons for students.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Nanoscience & Nanotechnology
Xuewen Guo, Jabor Rabeah, Ruixue Sun, Dengxu Wang, Esteban Mejia
Summary: A series of hybrid porous polymers (HPPs) based on polyhedral oligomeric silsesquioxane (POSS) were synthesized and successfully used as metal-free heterogeneous photocatalysts for cross-dehydrogenative coupling reactions, showing efficient catalytic performance under visible light. The novel catalysts can be easily recovered and reused, with mechanistic investigations revealing the oxidation-reduction process during photoexcitation.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Inorganic & Nuclear
Lars Hirneise, Dennis A. Buschmann, Caecilia Maichle-Moessmer, Reiner Anwander
Summary: The synthesis and properties of fluorenyl complexes of cerium were reported, including one, two, and three different fluorenyl ligand complexes. Different reaction conditions were explored to study the structural changes of these cerium complexes with fluorenyl ligands. It was found that Sigma-bond metathesis is the main reaction path for C-C bond formation in fluorenyl cerium complexes.
Review
Chemistry, Organic
Li Cheng, Quan Lin, Yunrong Chen, Hegui Gong
Summary: This review summarizes the recent developments on thermo-driven C(sp(3))-O bond radical scission methods and their applications in constructing C(sp(3))-C bonds. The focus is on the generation and transformation of radical intermediates under different approaches.
SYNTHESIS-STUTTGART
(2022)
Review
Chemistry, Multidisciplinary
Liangliang Song, Lingchao Cai, Lei Gong, Erik V. Van der Eycken
Summary: Copper-catalyzed enantioselective coupling reactions have been extensively studied for the rapid synthesis of chiral molecules. Despite progress in polar and radical mechanisms, the development of general and practical strategies for the regio-, enantio-, and diastereoselective assembly of stereogenic centers remains challenging. The integration of photocatalysis with asymmetric copper catalysis offers new reaction pathways and diverse chiral compounds, expanding the scope of radical chemistry. This review provides a summary of recent advances in photoinduced copper-catalyzed enantioselective coupling reactions, with a discussion on the mechanistic aspects.
CHEMICAL SOCIETY REVIEWS
(2023)
Editorial Material
Chemistry, Multidisciplinary
Nathan W. Dow
Summary: Nathan Dow is a third-year graduate student at Princeton University working in the lab of Prof. David MacMillan. His research focuses on combining photoredox activation with copper catalysis to achieve challenging chemical transformations through open-shell mechanisms.
Article
Multidisciplinary Sciences
Kenji Ota, Kazunori Nagao, Dai Hata, Haruki Sugiyama, Yasutomo Segawa, Ryosuke Tokunoh, Tomohiro Seki, Naoya Miyamoto, Yusuke Sasaki, Hirohisa Ohmiya
Summary: This study demonstrates a light-driven radical-polar crossover mechanism for the tertiary alkylation of phosphorus atoms in nucleotides, enabling the synthesis of alkylphosphonate structures that are difficult to obtain using existing methods.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Zijian Zhong, Pan Xu, Jinfeng Ma, Aihua Zhou
Summary: A green electrochemical oxidative cross-coupling protocol has been developed for the generation of thiosulfonates and sulfonate esters using sodium arenesulfinates and thiophenols/phenols. The reactions utilize inorganic and non-toxic NaI as redox catalyst and supporting electrolyte at room temperature without the need for oxidant and base, providing good yields of products and tolerating broad substrate scope. Mechanistic studies revealed that the reactions proceed via a radical pathway for the formation of SO2-S and SO2-O bonds.
Review
Chemistry, Multidisciplinary
Antonella lenia Alfano, Heiko Lange, Margherita Brindisi
Summary: The formation of amide bonds is essential in organic and synthetic medicinal chemistry. In recent years, the application of flow chemistry in amide bond formation has shown significant advantages and potential for development. This review summarizes and compares various methods and discusses future needs and prospects for sustainable synthesis.
Article
Chemistry, Physical
Jonas Elfert, Anup Bhunia, Constantin G. Daniliuc, Armido Studer
Summary: In this study, a radical transformation that enables intramolecular oxygen atom transfer to alkenes using the nitro functionality in nitroarenes as an oxygen donor is disclosed. The reaction proceeds via iron-catalyzed metal hydrogen atom transfer to alkenes and subsequent oxygenation, resulting in alkene hydration. Compared to intermolecular radical oxygenation, the intramolecular variant offers advantages, particularly in terms of diastereoselective radical hydration of conformationally flexible alkenes. The aryl moiety connecting the reactive NO2-functionality to the alkene substrate can be cleaved after oxygen transfer, yielding products derived from a formal diastereoselective intermolecular alkene hydration. Additionally, the resulting aniline entity after oxygen transfer can be used for the construction of nitrogen-containing heterocycles.
Article
Chemistry, Multidisciplinary
Ronghui Huang, Weijia Zhao, Shengwen Xu, Jingkai Xu, Chunxiao Li, Changsheng Lu, Hong Yan
Summary: A new synthesis method has been developed for the selective functionalization of nido-carboranes under metal-free conditions, leading to a series of nitrogen-containing nido-carboranes with moderate to good yields. This method represents a significant improvement for B-H functionalization of nido-carboranes with organic functionalities.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Alasdair K. Cooper, Megan E. Greaves, William Donohoe, Paul M. Burton, Thomas O. Ronson, Alan R. Kennedy, David J. Nelson
Summary: A nickel/dppf catalyst system successfully achieved Suzuki-Miyaura cross-coupling reactions of certain chloropyridines and chloroquinolines but not others, due to differences in the reaction mechanism. Chloropyridines rapidly undergo oxidative addition to the catalyst, while alpha-halo-N-heterocycles form catalytically inactive dimeric nickel species.
Article
Engineering, Chemical
Yeojin Kim, Yesol Woo, Hyeon Park, Youngmin Kim, Ho-Jeong Chae, Myung-June Park
Summary: This paper proposes a kinetic model for the chlorination of methane in the presence of a catalyst. The model accurately describes the experimental data and provides insights into the factors influencing the reaction.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2022)
Article
Chemistry, Physical
Ralf Kaiser, Long Zhao, Wenchao Lu, Musahid Ahmed, Marsel Zagidullin, Valeriy N. Azyazov, Alexander M. Mebel
Summary: Resonantly stabilized free radicals are considered fundamental molecular building blocks in the formation of polycyclic aromatic hydrocarbons and carbonaceous nanoparticles. Research has shown the formation of benzene and naphthalene through specific reactions at elevated temperatures, providing important insights into organic hydrocarbon chemistry in high temperature circumstellar environments and combustion systems.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Chenguang Liu, Mingyang Wang, Shihan Liu, Yujie Wang, Yong Peng, Yu Lan, Qiang Liu
Summary: The article reports on the non-noble metal-catalyzed asymmetric hydrogenation of N-heteroaromatics, quinolines. A new chiral pincer manganese catalyst showed outstanding catalytic activity in the reaction, producing high yields and enantioselectivities. The precise regulation of enantioselectivity was ensured by a pi-pi interaction, achieving competitive turnover numbers with noble metal catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Yunhu Han, Jun Dai, Ruirui Xu, Wenying Ai, Lirong Zheng, Yu Wang, Wensheng Yan, Wenxing Chen, Jun Luo, Qiang Liu, Dingsheng Wang, Yadong Li
Summary: The study presented a strategy to immobilize Ru atom using notched-polyoxometalate (N-POM) to prevent Ru aggregation during pyrolysis, leading to the successful synthesis of a Ru1@WOx/CN catalyst with outstanding catalytic activity for the hydrogenation of levulinic acid under solvent-free conditions. The N-POM strategy also shows potential in preparing a series of atomically dispersed noble-metal atoms, providing an opportunity for the discovery of single-atom catalysts.
Article
Chemistry, Organic
Jiaming Li, Jian Li, Xiaoliang Ji, Runfa He, Yang Liu, Zebin Chen, Yubing Huang, Qiang Liu, Yibiao Li
Summary: This study developed a reversible hydrogen-deuterium exchange reaction for nonactivated olefins, achieving reversible exchange between ordinary olefins and deuterated olefins. By using the lowest cost D2O without precious metal catalysts and ligands, a broad spectrum of functional groups compatibility was achieved.
Article
Chemistry, Multidisciplinary
Zhihui Shao, Shanshan Yuan, Yibiao Li, Qiang Liu
Summary: This study presents an efficient and sustainable synthetic route for the production of formaldehyde from renewable feedstock. The method involves the dehydrogenative cyclization of methanol as a formaldehyde surrogate, using a novel manganese catalyst, to synthesize N-heterocycles. The transformation shows high selectivity in trapping formaldehyde and avoids unwanted side reactions. Additionally, this method is successfully applied to the synthesis of C-13-labeled N-heterocycles.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Organic
Jian Li, Yang Liu, Zebin Chen, Jiaming Li, Xiaoliang Ji, Lu Chen, Yubing Huang, Qiang Liu, Yibiao Li
Summary: A method for obtaining substituted thiophenes with functional potential through metal-free dehydration and sulfur cyclization was described. The reaction of alkynols with elemental sulfur (S-8) or EtOCS2K yielded moderate-to-good yields. The method showcased the base-free generation of a trisulfur radical anion (S-3(center dot-)) and its addition to alkynes as an initiator. This research broadens the applications of S-3(center dot-) in the synthesis of sulfur-containing heterocycles.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Xufang Liu, Xianle Rong, Shihan Liu, Yu Lan, Qiang Liu
Summary: A novel method for the synthesis of chiral cyclic olefins, specifically 1-methylcyclohexenes, was reported in this study, enabling the construction of chiral compounds with diversified functionalities. The synthetic utility of this method was demonstrated by the concise and enantioselective synthesis of a natural product, beta-bisabolene, and further derivatizations showcased the versatility of the reaction products.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Chenguang Liu, Mingyang Wang, Yihan Xu, Yibiao Li, Qiang Liu
Summary: This study presents a Mn-catalyzed asymmetric hydrogenation of 3H-indoles, achieving high yields and enantioselectivities. The use of manganese catalyst allows for the compatibility of acid-sensitive functional groups, expanding the scope of this transformation and highlighting the uniqueness of earth-abundant metal catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Yujie Wang, Shihan Liu, Haobo Yang, Hengxu Li, Yu Lan, Qiang Liu
Summary: Research shows that a higher efficiency can be achieved by substituting an N-M' group (M' = alkali metals) for the N-H moiety using a large excess of metal alkoxides (M'OR), but the metal-hydride amidate intermediate has not yet been isolated. Furthermore, it is found that M/NM' bifunctional catalysis is superior to classic M/NH bifunctional catalysis in hydrogenation reactions.
Article
Chemistry, Multidisciplinary
Zeyuan Wei, Hengxu Li, Yujie Wang, Qiang Liu
Summary: The reactivity of metal-hydride complexes can be controlled by modifying ancillary ligands. In this study, a versatile and efficient NHC-based NNC-pincer Mn catalyst was designed to enhance the hydride-donor ability and reduce steric hindrance. The newly developed catalyst showed higher activity than the corresponding NNP-pincer Mn catalyst, enabling successful hydrogenation of a wide range of polar unsaturated compounds under mild conditions. This work presents a rare example of a general phosphine-free Mn-catalyzed hydrogenation system.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Bingxue Liu, Deguang Liu, Xianle Rong, Xi Lu, Yao Fu, Qiang Liu
Summary: A ligand-controlled stereoselective C-alkyl glycosylation reaction was reported for the synthesis of 2-deoxy-beta-C-alkyl glycosides from readily available glycals and alkyl halides. The method exhibits broad substrate scope and excellent diastereoselectivity under very mild conditions. In addition, a stereodivergent synthesis of 2-deoxy-C-ribofuranosides was achieved using different chiral bisoxazoline ligands.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Bingxue Liu, Qiang Liu
Summary: Cobalt-catalyzed hydroalkylation of alkenes and alkynes is an efficient method for selective formation of C-C bonds. Significant progress has been made in the past five years, covering different reaction mechanisms.
Article
Chemistry, Multidisciplinary
Bingxue Liu, Qiang Liu
Summary: In this study, we report a method for the reductive deoxygenation of ketones using a cobalt/Lewis acid catalyst and H-2 as the reductant. We discovered that the newly developed catalyst exhibits dual hydrogenation activities for both ketones and alkenes under the same reaction conditions. This method shows a broad substrate scope, excellent functional-group compatibility, and potential applicability.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Review
Chemistry, Organic
Liu Chenguang, Liu Qiang
Summary: The use of earth-abundant metal catalysts for asymmetric hydrogenation reactions has significant implications for sustainable synthesis of chiral nitrogen-containing fine chemicals, replacing the reliance on noble-metal catalysts.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Bingxue Liu, Yibiao Li, Qiang Liu
Summary: This study reports a novel cooperative cobalt/Lewis acid (LA)-catalyzed reductive etherification method using H-2 as the reductant, which can efficiently synthesize various ether molecules. The method demonstrates high selectivity and wide scope of application.
Article
Chemistry, Physical
Xufang Liu, Qiang Liu
Summary: Catalytic asymmetric olefin isomerization is an important reaction for the synthesis of enantioenriched olefinic compounds with biological activity and pharmaceutical value. Highly selective catalytic methods have been developed for the synthesis of challenging chiral olefins. This perspective summarizes the major advances in this field and discusses the mechanisms, scope and limitations, and opportunities for further development.
