Article
Chemistry, Multidisciplinary
Jingdong Wang, Yuxin Liu, Zhonglin Wei, Jungang Cao, Dapeng Liang, Yingjie Lin, Hai-feng Duan
Summary: A series of chiral thiourea compounds with multiple H-bond donors derived from hydroquinine have been reported. The aza-Henry reaction of isatin-derived ketimines and long-chain nitro-alkanes catalyzed by these chiral thioureas shows high enantioselectivity and excellent diastereoselectivity. This work represents the first report on long-chain nitroalkanes as substrates with excellent diastereoselectivity in metal-free catalytic systems.
Article
Chemistry, Multidisciplinary
Yanjun Li, Yan-Cheng Liou, Xinran Chen, Lutz Ackermann
Summary: A highly selective C-H olefination reaction was achieved using thioethers as the substrates and a palladium/chiral phosphoric acid catalytic system under ambient air. Axially chiral (hetero)biaryls were successfully synthesized, leading to a broad range of chiral heterocycles with excellent enantioselectivities up to 99% ee. Experimental and computational studies were conducted to understand the mechanism of this reaction and a plausible chiral induction model was proposed based on detailed DFT calculations.
Article
Chemistry, Organic
Zong-Ci Liu, Wen-Jun Yue, Liang Yin
Summary: In this study, a variety of novel unnatural chiral alpha-amino acid derivatives were synthesized via copper(I)-catalyzed asymmetric conjugate addition, showing moderate to high yields and high enantioselectivity. The reaction demonstrated good tolerance towards various azaarenes and electrophiles, providing the corresponding chiral alpha-amino acid derivatives in high (E)/(Z) ratio and high enantioselectivity. Most notably, the methodology was successfully applied in the catalytic asymmetric functionalization of Schiff bases derived from peptides, resulting in a new chiral tripeptide with high total yield and excellent stereo- and enantioselectivities.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Gabriele Lupidi, Alessandro Palmieri, Marino Petrini
Summary: A novel riboflavin-promoted reaction of primary nitroalkanes coupled with a nitroaldol reaction was discovered, enabling the synthesis of functionalized nitro alcohols under mild reaction conditions. However, secondary nitroalkanes were consumed under the reaction conditions without yielding the expected nitroaldol products.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Xinduo Sun, Chaoji Xiong, Fanrui Zhou, Kun Liang, Chunhua Wu, Xiaoping Rao, Qian Chen
Summary: The asymmetric addition of terminal alkynes catalyzed by a transition metal to isatins is an efficient and economical method for synthesizing 3-alkynyl-3-hydroxy-2-oxindoles. Using a new dimeric chiral quaternary ammonium derived from quinine as the cationic inducer, under mild conditions, the desired chiral compounds can be obtained in good to high yields with high enantioselectivity (<= 99% ee), and a variety of aryl-substituted terminal alkynes and substituted isatins are tolerated in this reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Sooyun Choi, Melody C. Guo, Gavin M. Coombs, Scott J. Miller
Summary: An atroposelective synthesis method for N-aryl 1,2,4-triazoles was developed. By utilizing a chiral phosphoric acid catalyst, a cyclodehydration reaction achieved asymmetric induction, resulting in atropisomeric N-aryl 1,2,4-triazoles with up to 91:9 enantiomeric ratio. Further crystallization of the isolated heterocycle enhanced the atropisomeric ratio of several analogs to 99:1 or higher. Additionally, a divergent and substrate-dependent reaction pathway leading to a different heterocyclic product was revealed.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Xian-Yun Huang, Pei-Pei Xie, Lei-Ming Zou, Chao Zheng, Shu-Li You
Summary: Here, we report a highly efficient synthesis method for enantioenriched aza-[3.3.1]-bicyclic enamines and ketones using indoles and azodicarboxylates through asymmetric dearomatization. The reaction involves electrophilic amination followed by aza-Prins cyclization/phenonium-like rearrangement. A newly developed fluorine-containing chiral phosphoric acid catalyst shows excellent activity in promoting this cascade reaction. The presence or absence of water directs the reaction towards enamine or ketone products, with high yields (up to 93%) and enantiopurity (up to 98% ee). DFT calculations reveal the energy profile, enantioselectivity, and water-induced chemoselectivity of the reaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Viraj A. Bhosale, Ivana Cisarova, Martin Kamlar, Jan Vesely
Summary: This study presents a novel chiral phosphoric acid (CPA)-catalyzed reaction, allowing for the asymmetric addition of alpha-fluoro(phenylsulfonyl)methane (FSM) derivatives to in situ generated cyclic N-acyliminium. The process demonstrates high stereoselectivity, leading to the formation of biorelevant isoindolinones containing sulfone and fluorine substituents with excellent stereoselectivities.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Naoki Yasukawa, Ami Yamanoue, Tsunayoshi Takehara, Takeyuki Suzuki, Shuichi Nakamura
Summary: The first enantioselective aza-Henry reaction of non-activated cyclic iminoesters, derived from cyclic amino acids, has been developed using a unique cinchona alkaloid sulfonamide/zinc(ii) catalyst. Good yields and enantioselectivities were observed, and the stereochemistry was explained by proposed transition state based on experiments and DFT calculations.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Fuxing Yang, Xingcui Zhou, Yongquan Wei, Lisheng Wang, Jun Jiang
Summary: This study successfully established an organocatalytic enantioselective 1,4-hydrophosphination reaction of in situ generated aza-o-quinone methides with H-phosphine oxides in the presence of simple and commercially available hydroquinine. The methodology provides an efficient route to a variety of optically active diarylmethyl phosphine oxides in moderate to good yields with good to excellent enantioselectivities, representing a unique example of asymmetric 1,4-conjugate addition of aza-o-quinone methides via C-P bond formation.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Xiaoxiao Song, Yanjun Fan, Zhiming Zhu, Qijian Ni
Summary: We have developed a highly straightforward strategy for the synthesis of a new axially chiral 3-arylindolizine scaffold using chiral phosphoric acid catalyst. The reaction showed good scalability and yielded a series of axially chiral 3-arylindolizines with excellent enantioselectivity. This approach not only has a broad substrate scope and mild reaction conditions, but also demonstrates the potential utility of the formed axially chiral compounds.
Article
Chemistry, Organic
Hongxiang Li, Qian Yang, Lei Xu, Jie Wei, Yurong Tang, Yunfei Cai
Summary: In this study, an asymmetric three-component rearrangement of alkenylfurans with various sulfonyl chlorides and anilines was developed via copper(I) and chiral vanadium cooperative catalysis, providing a facile access to a broad spectrum of sulfonylfunctionalized 4-aminocyclopentenones in high yields with excellent enantio- and diastereoselectivities.
Article
Chemistry, Organic
Cong-Yun Tang, Jie Wu, Feng-Ting Ji, Fang Tian, Lin Peng, Liang-Liang Wang
Summary: Enantioenriched tricyclic tetrahydropyran derivatives were successfully synthesized through chiral phosphoric acid catalyzed intramolecular reactions, with good yields and excellent stereocontrol. The high enantioselectivity is attributed to the rationally designed remote dual hydrogen bonding interaction, which effectively arranges the conformation of the flexible substrate.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Pier Alexandre Champagne
Summary: The first catalytic intermolecular desymmetrization of azetidines was reported in 2015, and Density Functional Theory calculations were used to uncover the mechanism and high enantioselectivity. The reaction proceeds through bifunctional activation of the azetidine nitrogen and the thione tautomer of the 2-mercaptobenzothiazole nucleophile. The selectivity is driven by the ability of the substrates to fit into the chiral catalyst pocket based on primary orbital interaction requirements.
Article
Chemistry, Organic
Bruno N. Falcone, Matthew N. Grayson
Summary: The study reported the first catalytic enantioselective aza-Cope rearrangement, achieving high yields and enantioselectivities. Using Density Functional Theory, the mechanism of the reaction and the origin of enantioselectivity were explained. Through conformational search and energy analysis, it was found that the Transition State leading to the major product had more interactions and stronger hydrogen bonds compared to the Transition State leading to the minor product.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Zheng-Jia Shen, Chen Zhu, Xiao Zhang, Chao Yang, Magnus Rueping, Lin Guo, Wujiong Xia
Summary: This article describes a selective (deutero)hydrodefluorination reaction via electrolysis, which achieves remarkable chemoselectivity control by the addition of different organoboron sources. The method is operationally simple, scalable, and provides access to high-value building blocks for medicinal chemistry in one step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Jose J. Delgado-Marin, Alejandra Rendon-Patino, Vijay Kumar Velisoju, Gadde Sathish Kumar, Naydu Zambrano, Magnus Rueping, Jorge Gascon, Pedro Castano, Javier Narciso, Enrique V. Ramos-Fernandez
Summary: We demonstrate that ZIFs used as catalysts for CO2 insertion suffer from irreversible degradation by leaching, leading to decreased stability and catalytic activity. Additional treatments are necessary to improve their stability.
CHEMISTRY OF MATERIALS
(2023)
Article
Multidisciplinary Sciences
Long Huang, Marcin Szewczyk, Rajesh Kancherla, Bholanath Maity, Chen Zhu, Luigi Cavallo, Magnus Rueping
Summary: In this study, stereodivergent allylic C(sp(3))-H bond arylations were successfully developed through a systematic investigation of the direction and degree of stereoselectivity in the cross-coupling process. Unlike the typical photosensitized geometrical isomerization of alkenes, the catalytic reaction demonstrated the feasibility of switching the C-C double bond stereoselectivity through ligand control and steric and electronic effects.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Sharath Kandambeth, Vinayak S. Kale, Dong Fan, Jeremy A. A. Bau, Prashant M. M. Bhatt, Sheng Zhou, Aleksander Shkurenko, Magnus Rueping, Guillaume Maurin, Osama Shekhah, Mohamed Eddaoudi
Summary: This work reports an innovative strategy for the synthesis of chemically robust metal-organic frameworks (MOFs) and their application as catalysts for the electrocatalytic oxygen evolution reaction (OER). The study demonstrates that bimetallic MOF systems with regulated metal ratios exhibit excellent catalytic activity and structural stability for OER.
ADVANCED ENERGY MATERIALS
(2023)
Article
Materials Science, Multidisciplinary
Jean Michel Merkes, Gerhard Raabe, Fabian Kiessling, Magnus Rueping, Srinivas Banala
Summary: The isolation and characterization of a kinetically stable oxadiazaborinine (ODB) dye are described in this study. It undergoes an unexpected thermal boron rearrangement, which results in a color change and increased fluorescence. This controllable reaction allows for the practical use as a time-temperature indicator probe, offering advantages such as photostability, non-reversibility, and environmental friendliness.
ADVANCED OPTICAL MATERIALS
(2023)
Article
Chemistry, Organic
Serik Zhumagazy, Chen Zhu, Huifeng Yue, Magnus Rueping
Summary: This article describes a nickel-catalyzed C-Se cross-coupling reaction between aryl iodides and selenols. The newly developed catalytic methodology provides easy access to various asymmetric selenium-containing compounds. The reaction exhibits excellent functional group tolerance, a wide range of substrates, high efficiency, and operates under mild conditions. Importantly, the protocol can be readily scaled up to gram-scale reactions without a loss of yield.
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.
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
Biotechnology & Applied Microbiology
Ram Karan, Dominik Renn, Shuho Nozue, Lingyun Zhao, Satoshi Habuchi, Thorsten Allers, Magnus Rueping
Summary: This study presents a genetic engineering and chemical modification approach to functionalize the major gas vesicle nanoparticle (GVNP) protein, GvpA. By introducing combinatorial cysteine mutagenesis within GvpA and expanding the N- and C-terminal regions, GvpA single, double, and triple cysteine variant libraries were generated. Thiol-maleimide chemistry was used to introduce biotechnologically relevant activities to the GVNPs. This approach significantly expands the bioengineering and functionalization potential of these novel protein nanomaterials.
JOURNAL OF NANOBIOTECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Wenhuan Huang, Chenyang Su, Chen Zhu, Tingting Bo, Shouwei Zuo, Wei Zhou, Yuanfu Ren, Yanan Zhang, Jing Zhang, Magnus Rueping, Huabin Zhang
Summary: The solar-driven evolution of hydrogen from water using particulate photocatalysts is a promising method for achieving a stable supply of renewable energy. However, the efficiency of photocatalytic water splitting is low due to sluggish electron-hole pair separation kinetics. In this study, highly oxidized Mo species incorporated into Cd0.5Zn0.5S nanorods exhibit significantly enhanced photocatalytic efficiency through inhibited electron-hole recombination.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Chunwei Dong, Ren-Wu Huang, Arunachalam Sagadevan, Peng Yuan, Luis Gutierrez-Arzaluz, Atanu Ghosh, Saidkhodzha Nematulloev, Badriah Alamer, Omar F. Mohammed, Irshad Hussain, Magnus Rueping, Osman M. Bakr
Summary: In this study, a synthesis method for obtaining an atomically precise nanoparticle with a surface-defective analogue is reported. The loss of a single surface atom drastically alters the reactivity of the nanoparticle, showing promising activity for click chemistry, especially photoinduced azide-alkyne cycloaddition. This study not only uncovers the effect of single-surface atom modification on nanoparticle properties but also demonstrates the potential of single-atom surface modification as a means for designing nanoparticle catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Editorial Material
Multidisciplinary Sciences
Huifeng Yue, Chen Zhu, Magnus Rueping
Review
Chemistry, Multidisciplinary
Jingchang Zhang, Magnus Rueping
Summary: In recent years, the combination of photocatalytic hydrogen atom transfer (HAT) and transition metal catalysis has become an important strategy for the synthesis of C(sp(3))-carbon and C(sp(3))-hetero bonds. This approach has been widely used in organic synthesis, leading to new transformations. This review summarizes the recent advances in sp(3) C-H functionalizations through photocatalytic HAT followed by transition metal catalysis, focusing on the diverse strategies, synthetic applications, and detailed mechanisms involved in these reactions. The understanding of these mechanisms is crucial for the rational design of new catalysts and reaction conditions to improve the efficiency of these transformations. We hope that this review will serve as a valuable resource for researchers in the field of metallaphotoredox catalysis and inspire further development in green chemistry, drug synthesis, material science, and other related fields.
CHEMICAL SOCIETY REVIEWS
(2023)