Article
Chemistry, Organic
Lenin Kumar Verdhi, Natalia Fridman, Alex M. Szpilman
Summary: A chiral nitroxide catalyst, generated in situ by a readily prepared chiral hydroxylamine precatalyst, in combination with a copper co-catalyst, serves as an environmentally friendly terminal oxidant for the enantioselective oxidative kinetic resolution of racemic axially chiral N-arylpyrrole alcohols, providing high enantioselectivity and reaction efficiency.
Article
Chemistry, Organic
Yiru Pu, Yi Zuo, Jie Ling, Meimei Li, Hui Huang, Chaozheng Zhang, Jirui Yang, Yun Deng, Maolin Wang, Jun Lu
Summary: An unprecedented strategy for NHC-catalyzed atroposelective amidation of lactams on racemic bispirooxindoles with enals has been developed, providing high yields and stereoselectivities. The reaction mechanism and origin of the enantioselectivity were investigated, indicating the importance of steric repulsion between oxindole and trimethylphenyl.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Jian Song, Wen-Hua Zheng
Summary: A highly enantioselective method for the kinetic resolution of racemic tertiary alcohols has been developed using chiral organotin-catalyzed intermolecular acylation. The process can be carried out under mild reaction conditions and has a broad substrate scope, allowing for the separation of the corresponding products and highly enantioselective recovery of tertiary alcohols with s factors up to >200.
Article
Chemistry, Organic
Soumen Barik, Rohan Chandra Das, Kuruva Balanna, Akkattu T. Biju
Summary: Chiral NHC-catalyzed kinetic resolution allows the synthesis of C-N axially chiral N-aryl aminomaleimides via remote chirality control. The reaction shows high stereoselectivity, yielding the desired product, and studies on C-N bond rotation and temperature dependence are provided.
Article
Chemistry, Multidisciplinary
Tay Zugman, Maria Clara da Silva Durigon, Suelem Kluconski Campos, Rodolfo Rodrigues da Silva, Thiago Sabino da Silva, Alfredo Ricardo Marques de Oliveira, Leandro Piovan
Summary: This study demonstrates the use of selenoesters as acyl donors in lipase-catalyzed enzymatic kinetic resolution of chiral alcohols. The results show that lipases can effectively cleave the C-Se bond of selenoesters, leading to the successful synthesis of enantiopure compounds. The enzymatic reaction is accelerated in an oxygen atmosphere, and the purification process is simple and easy.
Article
Chemistry, Multidisciplinary
Guanghui Wang, Lulu Li, Yifeng Jiang, Xiaowei Zhao, Xu Ban, Tianju Shao, Yanli Yin, Zhiyong Jiang
Summary: A chiral Bronsted acid catalysed phosphine-mediated deoxygenation protocol has been reported for the synthesis of azaarylethynyl tertiary alcohols and azaaryl-functionalized allenes, which are biologically and synthetically important derivatives. This metal-free method demonstrates high efficiency, excellent enantioselectivities, broad substrate scope, and practicality for the synthesis of deuterated allenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Hiroki Mandai, Ryuhei Shiomoto, Kazuki Fujii, Koichi Mitsudo, Seiji Suga
Summary: An efficient acylative kinetic resolution method for 3-hydroxy-3-substituted 2-oxindoles has been developed using a chiral DMAP derivative. The catalyst showed high efficiency with a wide range of substrates and could achieve high resolution within a short reaction time.
Article
Chemistry, Applied
Jianwen Jin, Lorenzo Carli, Yichao Zhao, Xuehua Zhu, Bo Xia, Philip Wai Hong Chan
Summary: This study presents a synthetic method for efficiently preparing enantioenriched secondary and tertiary 3-amido allylic alcohols. By utilizing stereoablative enantioselective kinetic resolution (KR) catalyzed by a chiral Brønsted acid, the researchers achieved product yields up to 50%, with ee and s values exceeding 99% and >200, respectively. The developed divergent catalytic protocol demonstrated excellent functional group tolerance and was further exemplified by the preparation of one tertiary example on a 1 mmol scale, followed by reduction or bromination to yield corresponding 1,3-amino alcohol and 2-bromo-1,3-amino alcohol derivatives.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Juan Liu, Yi-Ying Du, Yu-Shi He, Yan Liang, Shang-Zhong Liu, Yi-Yi Li, Yi-Ming Cao
Summary: In this study, a chiral phosphoric acid catalyzed apparent hydrolytic ring-opening reaction was developed for racemic aziridines in a regiodivergent parallel kinetic resolution manner. Through the acyloxy-assisted strategy, highly stereocontrolled nucleophilic ring-opening of aziridines with water was achieved, resulting in enantioenriched amino alcohols with high yields and enantiomeric ratios.
Article
Chemistry, Organic
Taichiro Touge, Hideki Nara, Michio Kida, Kazuhiko Matsumura, Yoshihito Kayaki
Summary: Efficient dynamic kinetic resolution of cyclic halohydrins was achieved by asymmetric transfer hydrogenation of racemic alpha-haloketones using bifunctional oxo-tethered Ru(II) catalysts. The catalyst could produce chiral alcohols with various functional groups with excellent diastereo- and enantioselectivities, providing a concise synthetic approach to a dopamine D3 receptor ligand, (+)-PHNO.
Review
Biotechnology & Applied Microbiology
Chenming Huang, Junling Liu, Jiali Fang, Xian Jia, Zhendong Zheng, Song You, Bin Qin
Summary: This review discusses the advances in the research area of KRED-catalyzed asymmetric synthesis for biomanufacturing of chiral chemicals with at least two chiral centers through the kinetic resolution (KR) approach and the dynamic kinetic resolution (DKR) approach.
FRONTIERS IN BIOENGINEERING AND BIOTECHNOLOGY
(2022)
Article
Multidisciplinary Sciences
Lin-Xin Ruan, Bo Sun, Jia-Ming Liu, Shi-Liang Shi
Summary: Despite the importance of enantioenriched tertiary alcohols bearing two contiguous stereocenters, their efficient synthesis has remained a challenge. In this study, we report a platform for their preparation using nickel-catalyzed addition of organoboronates to racemic ketones, achieving high levels of diastereo- and enantioselectivity.
Article
Chemistry, Multidisciplinary
Satoshi Horino, Tomoya Nishio, Shinji Kawanishi, Shinya Oki, Koichi Nishihara, Takashi Ikawa, Kyohei Kanomata, Karla Wagner, Harald Groeger, Shuji Akai
Summary: In this study, a method for obtaining S enantiomers from secondary 3-(trialkylsilyl)propargyl alcohols was achieved by using a well-known R-selective Pseudomonas fluorescens lipase in combination with a racemization catalyst VMPS4, in which the silyl group reverses the size relationship of substituents near the carbinol moiety. Immobilization of the lipase on Celite was found to be important for achieving a high efficiency of the dynamic kinetic resolution.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Muxing Zhou, Tatiana Gridneva, Zhenfeng Zhang, Ende He, Yangang Liu, Wanbin Zhang
Summary: This study presents an efficient route for the synthesis of chiral phthalidyl ester prodrugs using a chiral bicyclic imidazole organocatalyst and a continuous injection process. Computational studies suggest a general base catalytic mechanism different from the widely accepted nucleophilic catalytic mechanism. Analysis of key transition states reveals that CH-pi interactions, rather than previously considered cation/pi-pi interactions, play a dominant role in stereocontrol.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Multidisciplinary Sciences
Ayumi Imayoshi, Bhatraju Vasantha Lakshmi, Yoshihiro Ueda, Tomoyuki Yoshimura, Aki Matayoshi, Takumi Furuta, Takeo Kawabata
Summary: Since the discovery of mechanically planar chiral rotaxanes and topologically chiral catenanes, their asymmetric synthesis has been a long-standing challenge. Here, the authors report enantioselective preparation of mechanically planar chiral rotaxanes with up to 99.9% ee in 29% yield.
NATURE COMMUNICATIONS
(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
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)
Editorial Material
Multidisciplinary Sciences
Huifeng Yue, Chen Zhu, Magnus Rueping
Article
Nanoscience & Nanotechnology
David Ohayon, Dominik Renn, Shofarul Wustoni, Keying Guo, Victor Druet, Adel Hama, Xingxing Chen, Iuliana Petruta Maria, Saumya Singh, Sophie Griggs, Bob C. Schroeder, Magnus Rueping, Iain McCulloch, Sahika Inal
Summary: We developed an electrochemical transistor with an n-type conjugated polymer film for sensitive and selective glucose detection in bodily fluids. By studying the impact of the polymer chemical structure on film surface properties and enzyme adsorption behavior, we found that a negatively charged, smooth, and hydrophilic film surface provides the best environment for enzyme adsorption and maximizes sensor performance.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Saidkhodzha Nematulloev, Arunachalam Sagadevan, Badriah Alamer, Aleksander Shkurenko, Renwu Huang, Jun Yin, Chunwei Dong, Peng Yuan, Khursand E. Yorov, Azimet A. Karluk, Wasim J. Mir, Bashir E. Hasanov, Mohamed Nejib Hedhili, Naveen M. Halappa, Mohamed Eddaoudi, Omar F. Mohammed, Magnus Rueping, Osman M. Bakr
Summary: This study reports the synthesis of atomically precise copper hydride nanoclusters with a controlled defect, which were demonstrated to be highly selective catalysts for C-C cross-couplings. The work highlights the potential of defective nanoclusters as model systems for investigating individual defects, correlating defects with physicochemical properties, and rationally designing new nanoparticle catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Haifeng Chen, Chen Zhu, Huifeng Yue, Magnus Rueping
Summary: In this study, a nickel-catalyzed, three-component reductive protocol for group 14 element hetero-difunctionalization of 1,3-enynes using electrochemistry is described. The method is mild, selective, and general, allowing for the silyl-, germanyl-, and stannyl-alkylation of enynes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(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.
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)
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)
Article
Chemistry, Multidisciplinary
Chenyang Wang, Luis Miguel Azofra, Phong Dam, Edelman J. Espinoza-Suarez, Hieu Trung Do, Jabor Rabeah, Angelika Brueckner, Osama El-Sepelgy
Summary: In this study, an intramolecular endo-selective Heck reaction of iodomethylsilyl ethers of phenols and alkenols was reported. The reaction resulted in the formation of seven- and eight-membered siloxycycles in excellent yields, which could be further converted into the corresponding allylic alcohols upon oxidation. This method could be used for the selective (Z)-hydroxymethylation of o-hydroxystyrenes and alkenols. Rapid scan EPR experiments and DFT calculations suggested a concerted beta-hydrogen elimination event to take place in the triplet state.
CHEMICAL COMMUNICATIONS
(2023)
