Article
Chemistry, Multidisciplinary
Tongtong Jia, Di Meng, Ran Duan, Hongwei Ji, Hua Sheng, Chuncheng Chen, Jikun Li, Wenjing Song, Jincai Zhao
Summary: Prospects in light-driven water activation have led to rapid progress in hydrogenation reactions. In this study, a Ni2+-N-4 site built on carbon nitride was used for catalyzing the semihydrogenation of alkynes with water providing protons, powered by visible-light irradiation. Importantly, this photocatalytic approach enabled the production of diverse deuterated alkenes in D2O with excellent deuterium incorporation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yishu Jiang, Rafael Lopez-Arteaga, Emily A. Weiss
Summary: This study successfully extended the scope of quantum dot photocatalyzed cycloaddition reactions to substrates without anchoring groups by introducing polyaromatic energy shuttle molecules on the quantum dot surface, achieving high yields. Compared to traditional catalyst Ir(ppy)(3), it offers the advantages of lower catalyst loading, higher stability, and reusability.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Guanheng Huang, Jiayu Li, Ziqi Deng, Jinghong Li, Shanshan Sun, Liang Xu, Li Dang, Ming-De Li
Summary: The study demonstrates the generation of a stable dianion biradical through noncovalent interactions, which has the potential to serve as a photosensitizer under visible and NIR light excitation.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Shuoyan Xiong, Alexandria Hong, Brad C. Bailey, Heather A. Spinney, Todd D. Senecal, Hannah Bailey, Theodor Agapie
Summary: We address the challenge of insertion copolymerization of polar olefins and ethylene by designing ligands. The neutral nickel phosphine enolate catalysts with large phosphine substituents at the axial positions of Ni exhibit high activity and result in highly linear copolymers. The study reveals a strong correlation between axial steric hindrance and catalyst performance.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Barbara Klausfelder, Patricia Blach, Niels de Jonge, Rhett Kempe
Summary: This study reports a method for the synthesis of 3,4-dihydro-2H-pyrroles via the hydrogenation and cyclization of nitro ketones. The use of inexpensive and readily available starting materials allows for the flexible introduction of various substitution patterns. The reaction shows a broad scope and 23 out of the 33 synthesized compounds are previously unreported.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Teng Liu, Yin Liu, Wusheng Guo
Summary: This article describes the alkynyl-induced stereoselective construction of polysubstituted enynes via Pd-catalyzed allylic arylations. The interaction between the alkynyl group and the Pd-allyl fragment is proposed to be crucial for obtaining the desired products with exclusive (Z)-configurations.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Multidisciplinary Sciences
Yantao Li, Qianzhen Shao, Hengchi He, Chengjian Zhu, Xiao-Song Xue, Jin Xie
Summary: The authors present a method to synthesize tetrasubstituted olefins via dual photo- and nickel catalysis under an air atmosphere, without the need for an inert atmosphere. The synthesis of these compounds under mild conditions is challenging, but the authors were able to achieve it by using readily available carboxylic acids and alkenyl triflates. The method shows promise for applications in complex molecule modification and gram-scale synthesis.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Felix Glaser, Oliver S. Wenger
Summary: Combining the energy input from two red photons allows for chemical reactions that would normally require blue or ultraviolet irradiation. This biphotonic excitation strategy offers advantages such as deeper penetration and less photo-damage. By altering the photosensitizer in a dual photocatalytic system, the reaction outcome can be completely altered. Different biphotonic mechanisms lead to different photochemical reactivities, which can be controlled by changing the photosensitizer.
Article
Chemistry, Multidisciplinary
Hao Zhang, Congcong Huang, Xiang-Ai Yuan, Shouyun Yu
Summary: This research reports a photoexcited chiral copper complex that mediates enantioselective E -> Z isomerization, enabling kinetic resolution of 2-styrylpyrrolidines. The reaction expands the potential of kinetic resolution and provides a new reaction mode for enantioselective catalysis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Sheng-Qiang Guo, Hui-Qing Yang, Yu-Zhen Jiang, Ai-Lian Wang, Guo-Qiang Xu, Yong-Chun Luo, Zhao-Xu Chen, Haixue Zheng, Peng-Fei Xu
Summary: In this study, a green and reliable strategy for the diastereoselective synthesis of beta-amido sulfones through organophotoredox catalytic four-component radical-polar crossover cascade reactions was reported. The transformation exhibited excellent atom-, step-, and redox economy as well as diastereoselectivity.
Article
Engineering, Environmental
Mengxue Yang, Zexi Hou, Xin Zhang, Baoyu Gao, Yanwei Li, Yanan Shang, Qinyan Yue, Xiaoguang Duan, Xing Xu
Summary: In this study, the origins of selectivity in single-atom catalysts (SACs) based peroxymonosulfate (PMS) systems were investigated using experimental and theoretical approaches. The results showed that pollutants with high redox potential were primarily degraded by free radicals, while pollutants with low redox potential were predominantly degraded through the nonradical electron transfer pathway (ETP). Furthermore, the contribution of radical and nonradical pathways could be controlled by the loading of PMS.
ENVIRONMENTAL SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Multidisciplinary
Keishi Kohara, Aaron Trowbridge, Milo A. Smith, Matthew J. Gaunt
Summary: Visible-light-activated electron donor-acceptor complexes provide unique reaction pathways for the synthesis of complex molecules under mild conditions. This study demonstrates a method for the reductive generation of α-amino radicals through the reaction of a visible-light-activated ion-pair charge-transfer complex, allowing for the development of a multicomponent coupling reaction to form substituted aminomethyl-cyclopentanes. The operationally straightforward transformation is versatile and enables the generation of cyclic amine-containing scaffolds from readily available feedstocks.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Saikat Maiti, Joon Ho Rhlee
Summary: Stereoselective dicarbofunctionalization of terminal aryl alkynes has been achieved through reductive Ni-catalysis, utilizing alkyl iodide and aryl iodide as electrophilic coupling partners to accomplish exclusive regioselective and anti-addition selective alkylarylation.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Xiaodong Ma, Guozhu Zhang
Summary: This study describes a copper-catalyzed, highly enantioselective alkyl and aryl/azolation of alkenes, where the use of a specific chiral ligand plays a crucial role in the success of the chemistry. Anionic tridentate ligands are employed to enhance the reducibility of copper complexes, facilitating the generation of alkyl/aryl radicals and providing good enantiocontrol in the azolation. The three-component coupling reactions have mild reaction conditions and can tolerate a broad range of functional groups, allowing for the straightforward introduction of valuable azole functionalities into complex molecular systems through direct C-H functionalization.
Article
Chemistry, Multidisciplinary
Cui Wang, Florian Reichenauer, Winald R. Kitzmann, Christoph Kerzig, Katja Heinze, Ute Resch-Genger
Summary: This study achieved efficient green-to-blue upconversion by using the earth-abundant chromium complex [Cr(bpmp)(2)](3+), with a quantum yield close to the theoretical maximum, showing potential for practical applications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Jennifer Morvan, Francois Vermersch, Ziyun Zhang, Thomas Vives, Thierry Roisnel, Christophe Crevisy, Laura Falivene, Luigi Cavallo, Nicolas Vanthuyne, Guy Bertrand, Rodolphe Jazzar, Marc Mauduit
Summary: The development of highly efficient enantioselective olefin metathesis catalysts is a major challenge. By using optically pure chiral cyclic (alkyl)(amino)carbene (ChiCAAC) ligands and preliminary mechanistic insights and density functional theory (DFT) computations, it was observed that the formation of rotamers before the enantio-determining step can impair catalytic performances in this field. DFT calculations also demonstrated that these findings can help accelerate ligand discovery by providing faster methods to differentiate potential candidates.
Article
Multidisciplinary Sciences
Liuzhuang Xing, Qian Yang, Chen Zhu, Yilian Bai, Yurong Tang, Magnus Rueping, Yunfei Cai
Summary: In this study, the authors successfully incorporated privileged homogeneous bipyridyl-based Ni-catalysts into highly ordered and crystalline potassium poly(heptazine imide) (K-PHI), achieving the development goal of heterogeneous metallaphotocatalysis. The LnNi-PHI catalysts exhibit superior chemical stability and recyclability in C-P, C-S, C-O and C-N cross-coupling reactions.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Gadde Sathish Kumar, Chen Zhu, Rajesh Kancherla, Prashant S. S. Shinde, Magnus Rueping
Summary: An efficient method for the reductive cross-electrophile coupling of aziridines with aryl halides using nickel electrocatalysis is reported. Valuable phenethylamines are synthesized at room temperature in good yields. The reaction is distinct from conventional and photochemical couplings, and the role of Ni(II) organometallic complexes and electrodes in the reaction mechanism are examined.
Article
Chemistry, Physical
Manoj V. Mane, Sayan Dutta, Luigi Cavallo, Bholanath Maity
Summary: In recent years, there has been a growing interest in multicomponent reactions (MCRs) as environmentally friendly and reliable synthetic strategies for drug discovery. This article discusses theoretical investigations that unravel the mechanistic pathways in IrIII-CuII dual-catalyzed MCRs, experimentally reported by MacMillan, and explains the origin of selectivity between three-component and two-component coupling products. The results suggest that N-H bond activation is the rate-limiting step and the preference for a two-component product is governed by the relative stabilities of the CuII-X center dot intermediates.
Article
Chemistry, Physical
Zahra Almisbaa, Hassan A. Aljama, Khalid Almajnouni, Luigi Cavallo, Philippe Sautet
Summary: DFT-based reaction profiles and microkinetic simulations were used to investigate the selective hydrogenation of acetylene on Ni-based intermetallic catalysts. Among the tested catalysts, NiIn showed the highest ethylene yield, while NiIn and Ni2In3 exhibited reduced ethane formation and increased oligomerization compared to Ni and Ni3In. The findings emphasize the importance of considering oligomerization reactions and coverage effects when evaluating the selectivity of catalysts. Additionally, the presence of indium on the catalytic surface was found to decrease the rate of acetylene consumption, highlighting a trade-off between activity and selectivity.
Review
Chemistry, Physical
Sam Mathew, Dominik Renn, Magnus Rueping
Summary: Amine transaminases play a crucial role in the synthesis of chiral amines, which are essential building blocks in pharmaceuticals and fine chemicals. Advances in enzyme discovery, process engineering, and protein engineering have significantly enhanced the use of transaminases in organic synthesis. Enzymatic cascade engineering has emerged as an efficient and environmentally friendly approach for chiral amine synthesis, allowing the generation of valuable products from inexpensive starting materials. This review focuses on the utilization of amine transaminases in enzymatic and chemoenzymatic cascades for chiral amine synthesis.
Article
Chemistry, Physical
Haifeng Chen, Chen Zhu, Huifeng Yue, Magnus Rueping
Summary: An efficient cobalt-catalyzed carbon-germanium bond formation method has been developed, providing access to a wide range of functionalized germane-containing compounds. This method shows a broad scope and good tolerance toward various functional groups, and is conducted under mild reaction conditions. Mechanistic studies shed light on the unexpected reaction pathway and sequential activation of different electrophiles.
Article
Chemistry, Organic
Shiyi Yang, Xiang Yu, Yaxu Liu, Michele Tomasini, Lucia Caporaso, Albert Poater, Luigi Cavallo, Catherine S. J. Cazin, Steven P. Nolan, Michal Szostak
Summary: The Suzuki-Miyaura cross-coupling reaction enables the construction of biaryl ketones from inert amide bonds. However, the mechanism of C(acyl)-N bond oxidative addition and catalyst effect in this reaction remain poorly understood. This study investigates the use of [Pd(NHC)(sulfide)Cl-2] catalysts for amide N-C bond activation and presents the reaction development, kinetic studies, and reaction scope. DFT studies were also conducted to gain insight into the mechanism of C(acyl)-N bond oxidative addition and catalyst activation. The results suggest that [Pd(NHC)(sulfide)Cl-2] precatalysts could find application in C(acyl)-X bond activation in organic synthesis and catalysis.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Bholanath Maity, Sayan Dutta, Luigi Cavallo
Summary: C-sp3-C cross-coupling, a dream reaction in the chemical community, can be achieved by activating C-sp3-H bonds through visible light-induced transition metal-catalysis under mild reaction conditions. However, this research area is still in its early stages due to the chemical and technical complexity of this catalysis. Complementary experimental and theoretical mechanistic studies are essential for rational advances, as each approach alone is inadequate to clarify the operative mechanisms. In this tutorial review, we summarize representative experimental and computational mechanistic studies, highlighting the weaknesses, strengths, and synergies between the two approaches.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Rajesh Kancherla, Krishnamoorthy Muralirajan, Sayan Dutta, Kuntal Pal, Bo Li, Bholanath Maity, Luigi Cavallo, Magnus Rueping
Summary: The development of metal complexes that can function as both photocatalysts and cross-coupling catalysts is challenging. This study reports that divalent palladium can act as a light-absorbing species to achieve carbon-nitrogen cross-coupling reactions under air. Palladium acetate can be used as both the photocatalyst and cross-coupling catalyst for the selective cross-coupling amination of differently substituted aryl halides at room temperature.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Chao-Shen Zhang, Chang-Zhen Fang, Liang Yi, Chen Zhu, Zhi-Xiang Wang, Xiang-Yu Chen, Magnus Rueping
Summary: Visible light photoredox-catalyzed reactions are important in organic synthesis, but often require expensive photocatalysts. Charge transfer complex (CTC) photochemistry has emerged as an alternative, but substrate formation is necessary. In this study, we developed a new catalytic method using easily available N-heterocyclic nitreniums (NHNs) as photocatalysts. We demonstrated NHN catalysis for the photoreduction of C-Cl bonds, offering a simple and diverse transformation.
ORGANIC CHEMISTRY FRONTIERS
(2023)