Review
Chemistry, Multidisciplinary
Yaowen Liu, Pengfei Li, Yanwei Wang, Youai Qiu
Summary: Electrochemistry employs electrons as an efficient and sustainable alternative to chemical oxidants or reductants, and has gained popularity for selective organic synthesis. The combination of electrochemistry with readily available electrophiles has emerged as a viable method for constructing challenging C-C and C-heteroatom bonds. This mini-review provides a systematic summary of the recent advances in electroreductive cross-electrophile coupling (eXEC) reactions, focusing on aryl and alkyl organic (pseudo)halides, as well as small molecules such as CO2, SO2, and D2O.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Jordan L. S. Zackasee, Samir Al Zubaydi, Blaise L. Truesdell, Christo S. Sevov
Summary: Mediator-assisted electrocatalysis is a general strategy to enhance the electroreductive cross-electrophile coupling (eXEC) reactions. Addition of a redox-matched mediator enables the catalyst-mediator systems to generate products in near-quantitative yield. This study also identifies a library of catalyst-mediator systems that can couple a wide range of substrate classes in high yields.
Article
Chemistry, Organic
Bincy Chindan, Anagha Syam, Hariharan Mahendran, Ramesh Rasappan
Summary: In this study, a method for synthesizing α-vinyltrialkoxysilanes via cross-electrophile C(sp(2))-C(sp(2)) coupling was reported. The method demonstrates high compatibility with functional groups under milder reaction conditions.
Article
Chemistry, Organic
Xiaochun He, Jiangjun Liu, Gang Chen, Baojian Xiong, Xue Xiao, Lei Chen, Xuemei Zhang, Lin Dong, Xuelei Ma, Zhong Lian
Summary: A nickel-catalyzed cross-electrophile coupling of allylic acetates and gem-difluorovinyl tosylate has been developed. This reaction enables the synthesis of allylic gem-difluoroolefins via C(sp(3))-C(sp(2)) cross-electrophile coupling and proceeds under mild reaction conditions, providing a variety of allylic gem-difluorovinyl arenes in moderate to good yields. Mechanistic studies reveal the involvement of two different Ni(0)/Ni(II) catalytic cycles.
Article
Chemistry, Organic
Pete Delgado, Raoul J. Glass, Gina Geraci, Rohit Duvadie, Dyuti Majumdar, Richard Robinson, Imran Elmaarouf, Malte Mikus, Kian L. Tan
Summary: Facilitating photoredox coupling reactions in process-friendly green solvents was achieved by the successful application of a dual Ir/Ni catalyst system with enhanced solubility properties. This presentation highlights the benefits of altering the solubility properties of the ligands used in the Ir/Ni dual catalyst.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Grace A. Lutovsky, Samuel N. Gockel, Mark W. Bundesmann, Scott W. Bagley, Tehshik P. Yoon
Summary: In this study, a direct decarboxylative cross-coupling of native carboxylic acids with nucleophilic coupling partners mediated by inexpensive and non-toxic Fe(III) salts was reported. This method involves an initial photochemical decarboxylation followed by radical-polar crossover, enabling the construction of diverse carbon-carbon, carbon-oxygen, and carbon-nitrogen bonds with remarkable generality.
Article
Multidisciplinary Sciences
Wen Zhang, Lingxiang Lu, Wendy Zhang, Yi Wang, Skyler D. Ware, Jose Mondragon, Jonas Rein, Neil Strotman, Dan Lehnherr, Kimberly A. See, Song Lin
Summary: Recent research in medicinal chemistry has found a correlation between an increase in sp(3) carbons in drug candidates and their improved success rate in clinical trials. This study focuses on the development of robust and selective methods for constructing carbon(sp(3))-carbon(sp(3)) bonds. By using electrochemistry, the researchers achieve the selective activation of alkyl halides based on their electronic and steric properties, allowing for high selectivity in carbon(sp(3))-carbon(sp(3)) cross-electrophile coupling. This new protocol shows improved chemoselectivity and does not require a transition metal catalyst.
Article
Chemistry, Organic
Andrew C. Jones, William I. Nicholson, Jamie A. Leitch, Duncan L. Browne
Summary: The nickel-catalyzed cross-electrophile coupling of aryl halides and alkyl halides enabled by ball-milling is efficient and green, achieving reductive C-C bond formation under a mechanochemical manifold. The mechanical action provided by ball milling allows for the use of a variety of zinc sources to turnover the nickel catalytic cycle, resulting in the synthesis of 28 cross-electrophile coupled products.
Article
Chemistry, Organic
Haotian Sun, Baojian Xiong, Yuan Yang, Jiangjun Liu, Xuemei Zhang, Zhong Lian
Summary: A novel dual nickel/palladium-catalyzed reaction has been developed for the synthesis of compounds containing gem-difluorovinyl fragments, showing excellent stereoselectivity and yields. The method also exhibits good functional group tolerance.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Ya-Ting Wen, Xiang-Tao Kong, Hong-Chao Liu, Cui-Tian Wang, Wan-Xu Wei, Bin Wang, Xue-Yuan Liu, Yong-Min Liang
Summary: An innovative 1,5-HAT cascade strategy has been proposed for nickel-catalyzed distal arylation via cross-electrophile coupling. It selectively activates the remote C(sp(3))-H bond through specific migration and uses Ar-I as the available electrophile for constructing the C(sp(3))-C(sp(2)) bond. The method shows broad applicability for benzylic and aliphatic N-fluorocarboxamides with yields up to 80%. Control experiments suggest that this reaction may be initiated by a radical process.
Article
Chemistry, Multidisciplinary
Yubei Dai, Fang Wang, Shengqing Zhu, Lingling Chu
Summary: We describe a novel Ni-catalyzed three-component cross-electrophile coupling reaction for the synthesis of fluoroalkyl-incorporated 1,3-dienes. This method exhibits a broad substrate scope and excellent selectivity, providing a new organometallic agent-free platform for the construction of fluoroalkyl-incorporated diene motifs.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Linlin Ding, Yue Zhao, Hongjian Lu, Zhuangzhi Shi, Minyan Wang
Summary: For the first time, a catalytic enantioselective propargyl-aryl cross-coupling between two electrophiles was achieved in a stereoconvergent manner. The potential utility of this conversion is demonstrated in the facile construction of stereoenriched bioactive molecule derivatives and medicinal compounds based on the diversity of acetylenic chemistry. Detailed experimental studies have revealed the key mechanistic features of this transformation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Elizabeth R. Jarvo, Amberly B. Sanford
Summary: This article discusses the research conducted in the lab on the activation of alcohol derivatives in cross-coupling and cross-electrophile coupling reactions. The developed methods have enabled the use of secondary alcohols to produce tertiary stereogenic centers, which have been applied in the synthesis of pharmaceutically relevant compounds and substructures. The lab first focuses on the synthesis of bioactive compounds through stereospecific Kumada cross-coupling reactions and then discusses the development of a stereoselective cross-electrophile coupling reaction to synthesize cyclopropanes.
Article
Multidisciplinary Sciences
Haigen Fu, Jingzhe Cao, Tianzhang Qiao, Yuyin Qi, Simon J. Charnock, Samuel Garfinkle, Todd K. Hyster
Summary: This study reports a highly chemoselective and enantioselective Csp(3)-Csp(3) XEC reaction catalyzed by flavin-dependent 'ene'-reductases (EREDs). The photoexcitation of the enzyme-templated charge-transfer complex enables the chemoselective reduction of alkyl halides and high enantioselectivity.
Article
Chemistry, Multidisciplinary
Wendy L. Williams, Neyci E. Gutierrez-Valencia, Abigail G. Doyle
Summary: This paper reports the first branched-selective cross-coupling of 2-alkyl aziridines with aryl iodides using a Ti/Ni dual-catalytic system. The study demonstrates the tolerance towards functional groups and the effect of the steric and electronic profile on reactivity, resulting in predictive reactivity models and insights into the mechanism.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Biochemical Research Methods
Samuel Ellick, Christianne Wicking, Thomas Hancock, Samuel Whitmarsh, Christopher J. Arthur, Paul J. Gates
Summary: This study successfully applied field ionisation mass spectrometry and data science techniques to determine the ratio of different base oils in lubricant mixtures. This methodology can be applied to resolve the ratio of complex mixtures and has significant value in lubricant design.
RAPID COMMUNICATIONS IN MASS SPECTROMETRY
(2022)
Article
Chemistry, Physical
Yannik Appiarius, Philipp J. Gliese, Stephan A. W. Segler, Pascal Rusch, Jiangbin Zhang, Paul J. Gates, Rumpa Pal, Lorraine A. Malaspina, Kunihisa Sugimoto, Tim Neudecker, Nadja C. Bigall, Simon Grabowsky, Artem A. Bakulin, Anne Staubitz
Summary: Boron-nitrogen substitutions have a strong impact on the optical properties of polycyclic aromatic hydrocarbons (PAHs), but the observed properties also depend on intermolecular interactions. This study compared a thiophene-flanked BN-pyrene with its all-carbon analogue in solution and in the solid state, and found clear differences in their optical properties and crystal packing motifs.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Multidisciplinary
Y. A. N. N. I. K. APPIARIUS, A. N. N. E. STAUBITZ
Summary: 1,2-azaborinines, formed by replacing two neighboring carbon atoms in benzene with boron and nitrogen atoms, exhibit increased aromaticity compared to borazine. Experimental analysis of bond lengths, resonance stabilization energies, NMR shifts, and reactivities against electrophiles confirms this. Azaborinines, both monocyclic and polycyclic, have potential applications in materials science, pharmacology, and analytics due to their unique chemical, physical, and optical properties introduced by the polar B-N-unit.
CHEMIE IN UNSERER ZEIT
(2023)
Article
Chemistry, Organic
Souvik Ghosh, Christoph Eschen, Nadi Eleya, Anne Staubitz
Summary: This article presents the synthesis and functionalization of 12-membered azobenzene macrocycles (AzMs) to obtain meta- and para-aryl substituted AzMs. The substituents significantly impact the thermal stability of the less-stable Z isomers.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Materials Science, Multidisciplinary
Shuo Li, Ruchira Colaco, Anne Staubitz
Summary: Diazocine-functionalized initiators were synthesized for controlled radical polymerizations, and their efficiency in polymerizations of methyl acrylate and methacrylate was tested. The initiation of the reactions required high amounts of reducing agents and catalysts. Additionally, violet light irradiation during the reactions caused retardation or termination of the anilide compound.
ACS APPLIED POLYMER MATERIALS
(2022)
Article
Polymer Science
Shuo Li, Katrin Bamberg, Yuzhou Lu, Frank D. Soennichsen, Anne Staubitz
Summary: In this study, linear photoresponsive poly(thioether)s containing diazocine moieties in the polymer backbone were synthesized and their photoisomerization behavior was investigated. The resulting polymers showed reversible photoswitchability between the (Z)- and (E)-configurations. The study highlights the potential use of diazocine as an elongating actuator in macromolecular systems and smart materials.
Article
Chemistry, Multidisciplinary
Sven Schultzke, Nikolai Scheuring, Pim Puylaert, Matthias Lehmann, Anne Staubitz
Summary: A liquid crystalline polymer is designed to be bendable under visible light, allowing for safer and more efficient use in soft robotics, engineering, and biology.
Article
Chemistry, Inorganic & Nuclear
Yannik Appiarius, Pim Puylaert, Julius Werthschuetz, Tim Neudecker, Anne Staubitz
Summary: The isoelectronic relationship between 1,2-azaborinine and benzene is well known. By deprotonating 1,2-azaborinine, the anionic 1,2-azaboratabenzene is obtained, which has similar properties to pyridine. The study demonstrates the influence of formal boron substitution on the structure and electronic properties.
Article
Chemistry, Multidisciplinary
Melanie Walther, Waldemar Kipke, Raul Renken, Anne Staubitz
Summary: This study presents a novel method for stannylation and borylation of different positions of diazocines, which are azobenzene derived macrocyclic photoswitches with well resolved photostationary states. The results demonstrate their successful use in Stille cross-coupling and Suzuki cross-coupling reactions with organic bromides, achieving high yields.
Article
Chemistry, Multidisciplinary
Ester Maria Di Tommaso, Melanie Walther, Anne Staubitz, Berit Olofsson
Summary: This study developed a synthetic route to access ortho-substituted azobenzenes via novel ortho-substituted azobenzene-functionalized diaryliodonium salts. The selective transfer of the azobenzene moiety to various nucleophiles enables the synthesis of a wide range of ortho-substituted azobenzenes. The photoswitching properties and crystal structure of the reagents were investigated.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Souvik Ghosh, Christoph Eschen, Nadi Eleya, Anne Staubitz
Summary: This study presents the synthesis and versatile functionalization of 12-membered azobenzene macrocycles (AzMs). By introducing different substituents at different positions in the periphery, the thermal half-lives of the less-stable Z isomers can be significantly influenced. Meta-substitution leads to slower thermal relaxation compared to para-substitution, and electron-withdrawing groups result in slower relaxation than electron-donating groups.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Polymer Science
Ruchira Colaco, Clement Appiah, Anne Staubitz
Summary: In this study, Poly(N-isopropylacrylamide) PNIPAAm hydrogels were modified with a new azobenzene-containing co-monomer to achieve light responsiveness and two phase transitions controlled by light. The lower critical solution transition temperature (LCST) of the hydrogel was reduced by 12 degrees C through the incorporation of 2.5 mol% of the co-monomer. The LCST and structure of the hydrogel can be tuned by the hydrophobicity-hydrophilicity of the (E) and (Z) isomeric state of azobenzene. The large light-driven modulation of the LCST may have diverse applications in the field of soft robotics actuators.
Article
Chemistry, Multidisciplinary
Yannik Appiarius, Sandra Miguez-Lago, Pim Puylaert, Noah Wolf, Sourabh Kumar, Martin Molkenthin, Delia Miguel, Tim Neudecker, Michal Juriek, Araceli G. Campana, Anne Staubitz
Summary: The incorporation of boron-nitrogen units into polycyclic aromatic hydrocarbons improves their optical properties while retaining their geometries. The study found that helicenes with boron-nitrogen groups exhibited higher fluorescence quantum yield and outstanding luminescence dissymmetry, making them suitable candidates for circularly polarized luminescence emitters in materials science.
Article
Polymer Science
Laura Schumacher, Katharina Siemsen, Clement Appiah, Sunil Rajput, Anne Heitmann, Christine Selhuber-Unkel, Anne Staubitz
Summary: Hydrogels are biomaterials that can mimic the properties of biological tissues. This study introduces a new strategy to functionalize hydrogels by synthesizing a polymerizable linker that directly connects the polymeric structure with cell adhesion proteins. This allows for a uniform distribution of attachment sites throughout the hydrogel, enabling effective biofunctionalization.
