Article
Chemistry, Organic
Chen Zhang, Na-Na Ma, Zi-Lun Yu, Chuanji Shen, Xiaocong Zhou, Xue-Qiang Chu, Weidong Rao, Zhi-Liang Shen
Summary: The efficient palladium-catalyzed direct reductive cross-coupling reaction proceeds smoothly at room temperature with moderate to good yields, showing reasonable functional group tolerance. The one-pot reaction using readily available aryl bromide as a coupling partner is simple to handle, avoiding the use of pre-prepared organometallic reagents.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Xiaoshen Ma, Charles S. Yeung
Summary: Our study focused on achieving C(sp(2))-C(sp(3)) coupling reactions using 2,2-difluorobicyclo[1.1.1]pentane (BCP-F-2) building blocks. Through comparison of reactivities between BCP and BCP-F-2 analogues, we found that the Barluenga coupling reaction showed promising results, expanding the potential applications of BCP-F-2 in organic chemistry and medicinal chemistry.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Manjur O. Akram, John R. Tidwell, Jason L. Dutton, Caleb D. Martin
Summary: The synthesis of a single site neutral Lewis superacid, tris(ortho-carboranyl)borane (BoCb(3)), was achieved in one pot from commercially available materials. It was confirmed to be a Lewis superacid due to its high fluoride ion affinity (FIA), and exhibited stronger Lewis acidity compared to widely used fluorinated aryl boranes, as evidenced by the Gutmann-Beckett method and adducts with Lewis bases. The unusually high Lewis acidity can be rationalized by the electron-withdrawing effect of ortho-carborane and lack of pi-delocalization of the LUMO. Catalytic studies demonstrated that BoCb(3) is a superior catalyst for promoting C-F bond functionalization reactions compared to tris(pentafluorophenyl)borane [B(C6F5)(3)].
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Felipe Verdugo, Ricardo Rodino, Martin Calvelo, Jose Luis Mascarenas, Fernando Lopez
Summary: The reactivity of carbonyl-tethered alkylidenecyclopropanes (ACPs) can be directed towards tandem cycloisomerization/cross-coupling processes by using Pd-0 catalysts with phosphorus-based monodentate ligands. This allows for the synthesis of a wide variety of highly functionalized cyclic alcohols and amines through the formation of key pi-allyl oxapalladacyclic intermediates which are trapped with external nucleophilic partners.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Wei Chen, Wanzhi Chen, Miaochang Liu, Huayue Wu
Summary: The palladium-catalyzed Suzuki-Miyaura cross-couplings of nitroarenes and heteroarylboronate esters has been developed, leading to the synthesis of various heterobiaryl compounds. The practicality of this approach is demonstrated through the synthesis of druglike molecules.
Article
Chemistry, Physical
Yanhui Wang, Xiaotian Qi, Qiao Ma, Peng Liu, Gavin Chit Tsui
Summary: The diastereoselective synthesis of densely functionalized tetrasubstituted (E)-monofluoroalkenes via Pd(0)-catalyzed base-free Suzuki-Miyaura crosscouplings offers a significant method for producing pharmaceutically relevant compounds. Computational studies support the reaction design, revealing an intriguing mechanism of C-F bond activation leading to complete control of stereoselectivity. This method does not require extraneous base assistance, making it a powerful tool for stereocontrolled synthesis of monofluoroalkenes.
Article
Chemistry, Multidisciplinary
Wen-Duo Li, Yang Wu, Shi-Jun Li, Yi-Qian Jiang, Yan-Lin Li, Yu Lan, Ji-Bao Xia
Summary: A new strategy for direct cleavage of the C(sp3)-OH bond has been developed using neutral diphenyl boryl radical to activate free alcohols. Under mild visible light photoredox conditions, this strategy has been verified by cross-electrophile coupling of free alcohols and carbon dioxide to synthesize carboxylic acids. Control experiments and computational studies have shown that the activation of alcohols with neutral boryl radical leads to homolysis of the C(sp3)-OH bond, generating alkyl radicals, which can be further transformed into carbon anions for carboxylation with CO2 to form the coupling product.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Tobias Brueckner, Benedikt Ritschel, J. Oscar C. Jimenez-Halla, Felipe Fantuzzi, Dario Duwe, Christian Markl, Rian D. Dewhurst, Maximilian Dietz, Holger Braunschweig
Summary: Carbene-stabilized diborynes, including N-heterocyclic carbene (NHC) and cyclic alkyl(amino)carbene (CAAC), have been found to efficiently catalyze the intermolecular ortho-C-H borylation of N-heterocycles at room temperature. The reaction of NHC-stabilized diborynes with pyridine leads to the formation of a simple pyridyldiborene, while the combination of CAAC-stabilized diboryne with pyridine results in the activation of two pyridine molecules and the formation of a tricyclic alkylideneborane. Heating the alkylideneborane causes a further H-shift reaction, leading to the formation of a zwitterionic, doubly benzo-fused 1,3,2,5-diazadiborinine. Moreover, using quinoline as a substrate led to the formation of a borylmethyleneborane via an unprecedented boron-carbon exchange process.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jiajia Li, Junmin Chen, Hefeng Zhu, Mingzhong Cai
Summary: A new mesoporous SBA-15-anchored triphenylphosphine-gold(i) complex [SBA-15-Ph(3)PauNTf(2)] was synthesized and characterized. This catalyst allowed for the photosensitizer-free cross-coupling reaction of aryldiazonium tetrafluoroborates and alkynyltrimethylsilanes under blue LED irradiation, yielding diverse arylalkynes with good yields and high functional group tolerance. The catalyst could be easily recovered and reused multiple times without significant loss in activity.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Organic
Dmitry A. A. Dulov, Tatiana V. V. Magdesieva
Summary: It has been demonstrated that inexpensive and readily available N,N'-diaryldihydrophenazines can effectively replace Ir(III)- and Ru(II)-based photocatalysts in the dual photoredox/Ni(II)C-N coupling of aryl halides with a wide range of anilines, as shown by 32 examples. This efficient and operationally simple approach to diarylamines can be scaled up using a flow apparatus.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Shichao Li, Muyao Li, Shu-Sen Li, Jianbo Wang
Summary: A palladium-catalyzed stereoselective synthesis method has been developed for obtaining trans-alkenyl MIDA boronates from N-Methyliminodiacetyl boronate (BMIDA)-substituted N-tosylhydrazone and benzyl bromides. The products show moderate yields and good functional group compatibility, with potential applications in the synthesis of other boron-containing compounds or in cross-coupling reactions.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Avijit Roy, Martin Oestreich
Summary: The hydrosilylation of ketenes promoted by boron Lewis acid catalyst accelerates the reaction with hydrosilanes, providing access to a new class of aldehyde-derived silyl enol ethers. Moderate to high yields are obtained, with a preference for Z configuration.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Shuo Yang, Wei-Tao Jiang, Bin Xiao
Summary: The study focused on tertiary cyclopropyl carbagermatranes obtained through zinc-mediated decarboxylation, which showed efficient reactivity in palladium-catalyzed cross-coupling reactions. They also exhibited orthogonal reactivity with boron reagents, acting as robust nucleophiles for the synthesis of tertiary cyclopropane and efficient intermediates for quaternary center formation.
CHEMICAL COMMUNICATIONS
(2021)
Article
Multidisciplinary Sciences
Qiang Wei, Yuhsuan Lee, Weiqiu Liang, Xiaolei Chen, Bo-Shuai Mu, Xi-Yang Cui, Wangsuo Wu, Shuming Bai, Zhibo Liu
Summary: In this study, boronic acids were synthesized via photocatalytic decarboxylation of benzoic acids followed by borylation, with the assistance of guanidine-type additives. This simple process showed high step economy and good functional group compatibility, and a guanidine-based biomimetic active decarboxylative mechanism was proposed.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Vincent M. Kassel, Christopher M. Hanneman, Connor P. Delaney, Scott E. Denmark
Summary: Reaction conditions have been developed for refractory heteroaryl-heteroaryl Suzuki-Miyaura cross-couplings using neopentyl heteroarylboronic esters, heteroaryl bromides and chlorides, and potassium trimethylsilanolate (TMSOK) under anhydrous conditions. The addition of trimethyl borate enhances reaction rates by several mechanisms, enabling cross-coupling of diverse reaction partners in good yields and short reaction times.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Sinem Toksabay, Markus Leisegang, Andreas Christ, Patrick Haertl, Johannes Krebs, Todd B. Marder, Soumyajyoti Haldar, Stefan Heinze, Matthias Bode, Anke Krueger
Summary: The on-surface self-assembly of a bowl-shaped derivative on Cu(111) is reported, showing highly different arrangements at different temperatures. The formation process includes pi-stacked bowl-to-bowl dimers, chiral honeycomb structures, an intermediate trigonal superstructure, and a fully carbon-based, flattened hexagonal superstructure. This provides a potential precursor for holey graphene networks with unique defect structures.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Tong-Tong Liu, Jiaxin Chen, Bing-Tao Guan, Zhenyang Lin, Zhang-Jie Shi
Summary: Derived from structurally similar precursors, two different azidodiboranes underwent distinct aryl migration reactions triggered by different boron-boron separation distances. A shorter boron-boron distance led to heterolateral aryl migration and the formation of a seven-membered azadiborepin, while a longer boron-boron distance resulted in a stable bis-azidoborane scaffold. The pyrolysis of the bis-azidoborane led to the formation of an eight-membered oxazadiborocine through homolateral aryl migration and subsequent [3+2] cycloaddition. Density functional theory (DFT) calculations revealed that the boron-boron separation distances were the intrinsic factors driving the distinct migrations.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Wing Hei Marco Wong, Xueying Guo, Hok Tsun Chan, Tilong Yang, Zhenyang Lin
Summary: Heavier main-group element-catalyzed reactions have become an increasingly attractive tool for mimicking the behaviors of transition metal catalysts. The Bi-catalyzed synthesis of aryl sulfonyl fluorides reported by Magre and Cornella exhibits the ability of hypervalent coordination of the Bi(III) center and the high polarity of the Bi-Ph bond, allowing the heavier main-group element to resemble the transition metal in ligand association and dissociation flexibility. Additionally, the migrating Ph group's available pi electron pair stabilizes the SO2 insertion transition state by maintaining interaction with the Bi(III) center during migration.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Xin Xu, Zhenyang Lin
Summary: A mild synthetic method for transforming aromatic carbon-oxygen (C-O) bonds into useful molecules was reported. The method involved the use of a carbene complex to catalyze the asymmetric ring-opening reaction of dinaphthofuran with PhMgCl at room temperature. Density functional theory (DFT) calculations were performed to investigate the detailed mechanism, revealing a novel pathway involving Mg(II)-O coordination, phenyl nucleophile migration, and oxidative addition of a C-O bond to Ni(0). Insights into the role of the chiral NHC ligand in inducing enantioselectivity were also obtained.
Article
Chemistry, Multidisciplinary
Lukas Tendera, Felipe Fantuzzi, Todd B. Marder, Udo Radius
Summary: This study reports the synthesis of three nickel bis-boryl complexes and explores their bonding situation with the help of X-ray diffraction and DFT calculations. A delocalized, multicenter bonding scheme is observed in these complexes. The nickel complexes also show efficient catalysis in the diboration of alkynes, offering a different mechanistic pathway compared to platinum-catalyzed diboration. Stoichiometric reactions and DFT calculations are utilized to study the mechanism of the nickel-catalyzed alkyne borylation.
Article
Biochemistry & Molecular Biology
Lidija-Marija Tumir, Dijana Pavlovic Saftic, Ivo Crnolatac, Zeljka Ban, Matea Maslac, Stefanie Griesbeck, Todd B. Marder, Ivo Piantanida
Summary: A series of tetracationic bis-triarylborane dyes with different aromatic linkers showed high affinities towards ds-DNA and ds-RNA. The linker influenced the emissive properties of triarylborane cations and controlled the fluorimetric response of dyes. The different dye analogs exhibited selective or non-selective fluorescence responses and induced circular dichroism signals depending on the DNA/RNA sequences.
Article
Chemistry, Organic
Jianguo Hu, Shengchun Wang, Bin Li, Aiwen Lei
Summary: We report a protocol for constructing tetrahydroquinolines from bulk chemicals (alkenes and anilines) induced by K2S2O8. The method exhibits operational simplicity, wide scope, mild conditions, and a transition-metal-free system.
Article
Chemistry, Organic
Chang-Ming You, Cheng Huang, Sheng Tang, Peng Xiao, Shengchun Wang, Zhenhong Wei, Aiwen Lei, Hu Cai
Summary: Direct N-allylation of azoles with hydrogen evolution has been achieved by the synergistic combination of organic photocatalysis and cobalt catalysis. This protocol eliminates the need for stoichiometric oxidants and prefunctionalization of alkenes, and produces hydrogen (H2) as a byproduct. The transformation highlights high step and atom economy, high efficiency, and broad functional group tolerance, opening up a pathway for valuable C-N bond formation in heterocyclic chemistry.
Article
Chemistry, Inorganic & Nuclear
Rain Ng, Shun-Cheung Cheng, Ka-Lok Chan, Cheuk-Pui Leung, Wai-Man Cheung, Herman H. -Y. Sung, Hung Kay Lee, Chi-Chiu Ko, Ian D. Williams, Zhenyang Lin, Wa-Hung Leung
Summary: In this study, iridium complexes containing a bis-cyclometalated tripodal CANAC ligand were synthesized and their redox property and reactivity were investigated. Various iridium complexes were successfully obtained through different reactions, and their structures and properties were further studied. The results highlighted the crucial role of the CANAC ligand in stabilizing high-valent iridium.
Article
Multidisciplinary Sciences
Dongfeng Yang, Zhipeng Guan, Yanan Peng, Shuxiang Zhu, Pengjie Wang, Zhiliang Huang, Hesham Alhumade, Dong Gu, Hong Yi, Aiwen Lei
Summary: By electrochemical oxidative difunctionalization, the authors achieved functionalization of diazo compounds with two different nucleophiles. This method allows the synthesis of structurally diverse heteroatom-containing compounds, which are difficult to access by traditional methods, and display important synthetic applications. The reaction conditions are mild, exhibiting excellent functional group tolerance and efficiency for large-scale synthesis.
NATURE COMMUNICATIONS
(2023)
Review
Chemistry, Multidisciplinary
Wuyin Wang, Wentao Mo, Zishan Hang, Yueying Huang, Hong Yi, Zhijun Sun, Aiwen Lei
Summary: Transition metal element, copper, plays diverse and pivotal roles in oncology. It acts as constituents of metalloenzymes involved in cellular metabolism, function as signaling molecules to regulate the proliferation and metastasis of tumors, and are integral components of metal-based anticancer drugs. Notably, recent research reveals that excessive copper can also modulate the occurrence of programmed cell death (PCD), known as cuprotosis, in cancer cells.
Review
Chemistry, Multidisciplinary
Li Zeng, Jianxing Wang, Daoxin Wang, Hong Yi, Aiwen Lei
Summary: Organic electrosynthesis using alternating current (AC) is still in its early stages due to the lack of a comprehensive theoretical framework. This article provides an overview of recent advancements in AC-driven organic transformations and explores the differences between DC and AC electrolytic methodologies based on their physical principles. These differences include the prevention of metal catalyst deposition, precise modulation of oxidation and reduction intensities, and mitigation of mass transfer processes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Xingchen Liu, Haohua Chen, Dali Yang, Binjing Hu, Ying Hu, Shengchun Wang, Yu Lan, Aiwen Lei, Jie Li
Summary: A multicomponent sulfonylation reaction using sulfonyl chlorides and OPiv-supported organozinc reagents was achieved via cobalt-catalyzed alkene difunctionalizations. Anion-coordination played a critical role in modifying the reactivity and chemical properties of organozinc reagents. The OPiv-coordination resulted in the lower reducibility of arylzinc pivalates, allowing for the in situ formation of catalytically relevant Co(I) species as the active catalyst in carbosulfonylation reactions.
Article
Chemistry, Physical
Wenlong Sun, Chi-Ming Au, Ka-Wa Wong, Ka Lok Chan, Cheuk Kit Ngai, Hung Kay Lee, Zhenyang Lin, Wing-Yiu Yu
Summary: Directarene C-H functionalization by amidyl radicals has made significant progress for arylamides synthesis. Photocatalytic protocols can easily generate amidyl radicals under mild conditions, but designing catalysts with earth-abundant Fe complexes for C-H amidation is an attractive approach for controlling selectivity. However, the preference for high-spin configuration makes it challenging to design robust Fe catalysts for C-H amidation.
Article
Chemistry, Medicinal
Marta Jurkovic, Matthias Ferger, Isabela Draskovic, Todd B. Marder, Ivo Piantanida
Summary: This study presents a novel triarylborane (TB)-dye that serves as both an NMe2 pi-donor and an inductive NMe2-alkyl cationic acceptor. The TB-dye is highly sensitive to a click reaction with an azide-substituted lysine side chain, resulting in a significant red shift of emission. Furthermore, the TB-dye exhibits high affinities towards both DNA and proteins, making it an ideal fluorimetric probe for detecting the progress of click reactions and sensing the binding site composition.
