Review
Chemistry, Multidisciplinary
Vignesh Palani, Melecio A. Perea, Richmond Sarpong
Summary: This review discusses strategies for site-selective functionalization of polyhalogenated arenes and heteroarenes, including traditional reaction types and emerging strategies.
Article
Chemistry, Applied
Mikinao Koishi, Kazuki Tomota, Masaaki Nakamoto, Hiroto Yoshida
Summary: We report the direct Suzuki-Miyaura coupling of saturated organoboron compounds with dan substituents. Despite the reduced Lewis acidity of the boron center, cyclopropyl-B(dan) can be activated by t-BuOK to undergo transmetalation with a palladium complex. The increased s-character of the C-B(dan) bond is likely crucial for this reaction.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Ting Cui, Yanling Zhan, Changhui Dai, Jun Lin, Ping Liu, Peipei Sun
Summary: An electrochemical oxidative regioselective C-H cyanation of imidazo[1,2-a]pyridines was developed utilizing TMSCN as the cyano source, with the KH2PO4/K2HPO4 buffer being essential for the transformation. This protocol was compatible with a broad range of substituted imidazo[1,2-a]pyridines and provided the C3 cyanated products in moderate to excellent yields.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Zi-Tong Pan, Xu-Kuan Qi, Qian Xiao, Xi-Wen Liang, Jian-Ji Zhong, Jing-Xin Jian, Qing-Xiao Tong
Summary: In this study, we have demonstrated a regulable cross-coupling reaction using alcohols as alkylating reagents to functionalize benzothiazoles. We obtained two types of cross-coupling products with high isolated yields, opening up a broad research prospect for expanding alcohols as alkylating reagents.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Guang-Yan Xing, Ya-Cheng Zhu, Deng-Yuan Li, Pei-Nian Liu
Summary: On-surface synthesis, a powerful tool for atomically precise fabrication of low-dimensional carbon nanomaterials, has greatly enriched fundamental science and technology. Achieving high selectivity of covalent coupling reactions remains challenging due to the complicated reactivity of organic groups and irreversibility of covalent bonds. Only a few on-surface covalent coupling reactions are frequently used, and this Perspective focuses on the development and synthetic applications of on-surface cross-coupling reactions.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Dingyi Wang, Mingjie Li, Xiangyang Chen, Minyan Wang, Yong Liang, Yue Zhao, Kendall N. Houk, Zhuangzhi Shi
Summary: This study presents a method for selective silacyclization of (hetero)arenes using a convenient and stable silicon reagent via twofold C-H activation. The ODCS reagent is compatible with N-containing heteroarenes and can be used for silacyclization of various substrates. Mechanistic experiments and DFT calculations were conducted to investigate the preferred pathway for this twofold C-H activation process.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Xinlan A. F. Cook, Loic R. E. Pantaine, David C. Blakemore, Ian B. Moses, Neal W. Sach, Andre Shavnya, Michael C. Willis
Summary: Heteroaromatic sulfinates are effective nucleophilic reagents in Pd-0-catalyzed cross-coupling reactions with aryl halides. Base-activated, latent sulfinate reagents, such as beta-nitrile and beta-ester sulfones, have been introduced to address challenges in purifying and solubilizing metal sulfinate salts, as well as their tolerance to multi-step transformations. These latent sulfinate reagents have proven to be stable through multi-step substrate elaboration and amenable to scale-up processes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Renhe Li, Guangbin Dong
Summary: A new reaction mode of palladium/norbornene cooperative catalysis has been reported, involving the selective coupling of two different carbon-based electrophiles for vicinal double C-H functionalization of five-membered heteroarenes. The use of alkynyl bromides as the second electrophile allows for the vicinal difunctionalization of a wide range of heteroarenes including pyrroles, thiophenes, and furans at their C4 and C5 positions. This method has shown synthetic utility in preparing thiophene-containing organic materials and a protein kinase inhibitor analogue.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jun Chen, Yu-Jie Liang, Peng-Zi Wang, Guo-Qing Li, Bin Zhang, Hao Qian, Xiao-Die Huan, Wei Guan, Wen-Jing Xiao, Jia-Rong Chen
Summary: This study presents a photoinduced copper-catalyzed cross-coupling reaction for the generation of allylic esters. The reaction proceeds at room temperature with high regio- and enantioselectivity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Review
Chemistry, Multidisciplinary
Myuto Kashihara, Yoshiaki Nakao
Summary: Cross-coupling reactions using nitroarenes as electrophiles have gained attention due to their ease of accessibility and potential advantages over haloarenes. Recent research has focused on developing new catalyst systems and reaction conditions to improve the efficiency and practicality of these reactions, with promising results in diversifying bond-forming reactions and reducing catalyst loading. Research in this field is expected to continue growing as the utility of nitroarenes in organic synthesis is reevaluated.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Multidisciplinary
Maorui Wang, Chengqian Zhang, Chenggang Ci, Huanfeng Jiang, Pierre. H. Dixneuf, Min Zhang
Summary: Despite the challenges, we have successfully developed a room temperature approach for the direct construction of alpha-hydroxyalkyl cyclic amines through the strategy of electroreductive alpha-hydroxyalkylation. This method offers a broad substrate scope, simplicity in operation, high chemoselectivity, and does not require pressurized H2 gas or transition metal catalysts. The activation of reactants by the zinc ion generated from anode oxidation plays a crucial role in this transformation. This strategy, combined with substrate activation by Lewis acids, is expected to lead to the development of more useful transformations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Multidisciplinary
Xinlan A. F. Cook, Antoine de Gombert, Janette McKnight, Loic R. E. Pantaine, Michael C. Willis
Summary: This review focuses on the methods developed for the challenging coupling of 2-pyridine nucleophiles with (hetero)aryl electrophiles, ranging from traditional cross-coupling processes to alternative nucleophilic reagents and novel main group approaches.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jacob O. Rothbaum, Alessandro Motta, Yosi Kratish, Tobin J. Marks
Summary: Chemo-divergent synthetic methodologies are important in introducing structural diversity into organic products. This study reports the selective organolanthanide-catalyzed alpha-mono-borylation of 18 pyridines, resulting in the formation of valuable precursors for subsequent functionalization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Zhong Liu, Jia-Hao He, Ming Zhang, Zhu-Jun Shi, Han Tang, Xin-Yue Zhou, Jun-Jie Tian, Xiao-Chen Wang
Summary: This study reports a borane-catalyzed tandem reaction method that achieves exclusively C3-selective alkylation of pyridines, providing a practical tool for late-stage functionalization of structurally complex pharmaceuticals bearing a pyridine moiety.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Applied
Linhao Liu, Henri Doucet
Summary: The reactivity of 1,2-dihalobenzenes in palladium catalyzed polyheteroarylation via C-H bond functionalization was investigated. The first catalytic cycle using thiophene as the heteroarene gives the expected 2-(2-bromophenyl)thiophenes. In the course of the second catalytic cycle, in the presence of heteroarenes having a free C3-position, a partial Pd-1,4-migration occurred giving rise to aryl-substituted biheteroarenes such as 2 '-aryl-2,3 '-bithiophenes as well as the expected 1,2-di(thiophen-2-yl)benzenes. The best selectivities in favor of the formation of 2 '-aryl-2,3 '-bithiophenes were obtained with electron-rich 1,2-dihalobenzenes. A wide variety of thiophene derivatives bearing useful functions such as formyl, acetyl, cyclopropylmethanone, 2-methyl-1,3-dioxolane, ester, nitrile or chloro was tolerated allowing to prepare poly-functionalized 2 '-aryl-2,3 '-bithiophenes. Moreover, this one pot preparation of 2 '-aryl-2,3 '-bithiophenes employs a low loading of an air stable commercially available palladium source associated to an inexpensive base.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Review
Chemistry, Multidisciplinary
Yan Zhang, Zhenzhi Cai, Svenja Warratz, Chanchan Ma, Lutz Ackermann
Summary: In recent years, electrochemical oxidative reactions using radical intermediates have become an environmentally friendly and powerful method for the formation of C-E (E = C, N, S, Se, O and Hal) bonds through single-electron transfer processes at the electrodes. This minireview focuses on the recent advances in electrooxidation and radical reactions, particularly concerning radical additions onto alkynes, until June 2022.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Xinran Chen, Hasret Can Guelen, Jun Wu, Zi-Jing Zhang, Xin Hong, Lutz Ackermann
Summary: Ruthenium-catalyzed sigma-bond activation-assisted meta-C-H functionalization has gained significance in the formation of distal C-C bonds. However, the lack of mechanistic studies has hindered a complete understanding of the site-selectivity and reaction pattern. In this study, computational investigations were conducted on ruthenium-catalyzed C-H functionalization using alkyl bromides and aryl bromides. Monocyclometalated ruthenium(II) complexes were identified as the active species, with inner-sphere single electron transfer (ISET) facilitating the activation of organic bromides. The competition between reductive elimination and radical coupling determines the site-selectivity, which was further predicted using a multilinear regression model validated by experiments.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yan Zhang, Chunhang Zhao, Chanchan Ma, Zhenzhi Cai, Lutz Ackermann, Sven Trienes
Summary: We describe a mechanistically distinct approach using photoinduced carbon-carbon (C-C) activation/ring-opening to access gamma,delta-unsaturated aldehydes from methylenecyclobutanols and sulfonyl chlorides by strain release. The sulfonyl motif on the products was easily removed by another photocatalytic process, enabling the concise assembly of the natural product alatanone A. Our approach demonstrates versatile functional group tolerance, ample substrate scope, and scalability, and represents a conceptually distinct alternative to existing approaches for remote 1,4-diversifications, with a double bond remaining in the obtained products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Shan Chen, Binbin Yuan, Yulei Wang, Lutz Ackermann
Summary: By difunctionalization of nonactivated alkenes, twofold distal C-H functionalization was achieved, allowing rapid access to multifunctionalized molecules. The multicomponent ruthenium-catalyzed remote 1,n-difunctionalization (n=6,7) of nonactivated alkenes with fluoroalkyl halides and heteroarenes in a modular manner was reported. This method provided mild conditions, unique selectivity, and broad substrate scope, and featured a domino process for twofold remote C(sp(2))-H/C(sp(3))-H activation with the sequential formation of three different carbon-centered radicals. A plausible mechanism was proposed based on detailed experimental and computational studies.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jun Wu, Wen Wei, Julia Poehlmann, Rajeshwaran Purushothaman, Lutz Ackermann
Summary: In this study, a ruthenium(II)-catalyzed multicomponent Domino reaction was reported, which enables the efficient synthesis of structurally diversified C-alkyl glycosides in a single step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Dingyi Wang, Binbin Yuan, Jiawei Xu, Lutz Ackermann
Summary: In this study, an electrochemical strategy was used to achieve the dual functionalization of unactivated alkenes through an intramolecular migration process. This strategy eliminated the need for sacrificial chemical oxidants and noble-metal catalysts, and the reactions were carried out under mild conditions. The electrochemistry enabled the migration of (hetero)aryl groups, leading to the formation of alkenyl/alkynyl-migration products. The reaction mechanism was established through experiments and computations.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Editorial Material
Chemistry, Organic
Lutz Ackermann, Song Lin
Summary: The field of organic electrosynthesis and electrocatalysis has experienced a remarkable revival in recent years. Electrochemistry, as an unconventional reaction tool, has allowed synthetic chemists to innovate novel transformations, advance new synthetic strategies, and enhance the sustainability of organic synthesis.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Kui Zeng, Ruhuai Mei, Sebastian Dechert, Lutz Ackermann, Kai Zhang
Summary: This study reports a recyclable stereoauxiliary aminocatalytic approach for the efficient one-pot synthesis of desired trisubstituted indolizine-2-carbaldehydes via [3+2] annulations of acyl pyridines and alpha,beta-unsaturated aldehydes, using aminosugars derived from biomass. Control experiments confirm the stereoauxiliary effect favored by the beta-anomer of D-glucosamine. Moreover, polymeric chitosan containing predominantly beta-D-anhydroglucosamine units shows excellent catalytic performance and can be used for large-scale synthesis and catalytic cycling experiments. Thus, this approach advances the existing methodologies and provides a rich library of indolizine-2-aldehydes, which can be used for late-stage diversification and targeted modifications of bioactive molecules or drugs.
COMMUNICATIONS CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Yulei Wang, Suman Dana, Hao Long, Yang Xu, Yanjun Li, Nikolaos Kaplaneris, Lutz Ackermann
Summary: Late-stage functionalization (LSF) is a powerful strategy to accelerate the development of medicinally relevant compounds, crop protecting agents, and functional materials. Electrochemical late-stage functionalization (eLSF) has emerged as an environmentally friendly platform and has gained significant momentum in the past decade.
Article
Chemistry, Multidisciplinary
Elisa Y. Lai, Binbin Yuan, Lutz Ackermann, Magnus J. Johansson
Summary: In this study, a new method for directed ruthenium-catalyzed C-H aminocarbonylation has been developed under mild conditions through high-throughput experimentation. This method allows the introduction of special amide functional groups and is applicable to various substitution patterns and different weakly Lewis basic directing groups in anilides.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Agnese Zangarelli, Binbin Yuan, Lutz Ackermann
Summary: The first electro-C7-alkenylation of indoles is reported in this study, providing highly selective access to the C7 position. This sustainable method avoids the use of toxic and expensive chemical oxidants and allows for versatile product diversification.
ISRAEL JOURNAL OF CHEMISTRY
(2023)
Article
Meteorology & Atmospheric Sciences
S. P. Alexander, A. Protat, A. Berne, L. Ackermann
Summary: Antarctic precipitation, especially within the boundary layer, is poorly characterized and understood due to limited surface-based remote sensing observations. This study used cloud and precipitation remote-sensing instruments to characterize snowfall over Davis. The results reveal the relationship between virga and wind conditions, particle aggregation at certain temperatures, and the sublimation of snowfall mass at different altitudes. These findings contribute to a better understanding of snowfall in the Antarctic region.
JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES
(2023)
Article
Chemistry, Physical
Julia Struwe, Lutz Ackermann
Summary: In recent years, photoelectrocatalysis has become more and more viable for molecular synthesis. However, there is still a lack of detailed comparison among different catalysts for the undirected C-H functionalization of arenes. To address this, more than a dozen different mediators were utilized to compare their efficacies in the trifluoromethylation of (hetero-)arenes.
FARADAY DISCUSSIONS
(2023)
Article
Chemistry, Multidisciplinary
Isaac Maksso, Ramesh C. Samanta, Yifei Zhan, Kai Zhang, Svenja Warratz, Lutz Ackermann
Summary: The chemical up-cycling of polymers into value-added materials provides an opportunity for a circular economy. This study demonstrates the selective up-cycling of polystyrenes and polyolefins to C(sp(3))-H azidated materials through chemo-selective mangana-electrocatalysis. The functionalized polymers obtained showed high mass retention and functionalization. The electrocatalysis approach proved to be scalable and has implications for a green hydrogen economy.
Article
Chemistry, Multidisciplinary
Tsuyoshi Oyama, Lorena Mendive-Tapia, Verity Cowell, Adelina Kopp, Marc Vendrell, Lutz Ackermann
Summary: Fluorescent labeling of peptides catalyzed by non-toxic manganese(i) via C(sp(2))-H alkenylation enables the selective and site-specific labeling of peptides, providing access to novel near-infrared nitrobenzodiazole-based peptide fluorogenic probes.
