Letter
Chemistry, Organic
Na-Na Ma, Xuan-Bo Hu, Yuan-Shuai Wu, Ya-Wen Zheng, Mengtao Ma, Xue-Qiang Chu, Hao Xu, Haiqing Luo, Zhi-Liang Shen
Summary: A direct cross-coupling reaction of aryl thioether with aryl bromide was successfully achieved using nickel salt, magnesium, and lithium chloride as catalysts in tetrahydrofuran solvent at room temperature. The one-pot reactions efficiently cleaved the C-S bond, yielding the desired biaryls in moderate to good yields, without the need for pregenerated or commercial organometallic reagents.
Article
Chemistry, Organic
Alexis L. Gabbey, Nicholas W. M. Michel, Jonathan M. E. Hughes, Louis-Charles Campeau, Sophie A. L. Rousseaux
Summary: In this study, a new strategy was reported for the synthesis of secondary α-aryl amides through a nickel-catalyzed reductive arylation reaction using N-hydroxyphthalimide (NHP) esters of malonic acid half amides as redox-active substrates. This method proceeds under mild conditions and exhibits excellent chemoselectivity for amide α-arylation in the presence of other enolizable carbonyls.
Article
Chemistry, Applied
Sara Payamifar, Foad Kazemi, Babak Kaboudin
Summary: This study introduced a convenient nickel-catalyzed protocol for the Suzuki-Miyaura coupling reaction using a simple mixture of Ni(II) and unfunctionalized beta-cyclodextrin in water. The environmentally friendly and cost-efficient method allows the synthesis of biaryls from arylboronic acids and various aryl halides. The catalyst can be recycled for multiple runs with only a small decrease in catalytic activity.
APPLIED ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Yan-Yan Guan, Xiao-Xue Wu, Yu-Fang Liu, Jian-Bin Chao, Zhen-Kang Wen
Summary: A palladium-catalyzed desulfurative coupling of allylthioethers with organoboronic acids is described, which shows high chemoselectivity and good functional group tolerance, enabling the synthesis of a wide range of alpha-branched enones under mild reaction conditions. This method also provides a new retrosynthetic disconnection to multifunctionalized allylic molecules via selective cleavage of the C-S bond, serving as a complementary allylation protocol to Tsuji-Trost reactions.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Long Yin Lam, Cong Ma
Summary: A Chan-Lam-type C-S coupling reaction using sodium aryl sulfinates has been developed to provide diaryl thioethers in high yields with the presence of a copper catalyst and potassium sulfite. The mechanistic study revealed that potassium sulfite was involved in the deoxygenation of sulfinates through a radical process.
Article
Chemistry, Organic
Jin Zhang, Xin Wang, Jiale Liu, Xiaogang Wang, Xinkan Yang, Qun Zhao, Yangmin Ma, Ran Fang, Michal Szostak
Summary: Here, we report a mild Ru(0)-catalyzed cleavage of C(aryl)-O bonds enabled by a combination of a Ru-3(CO)(12) catalyst and an imine auxiliary. This method offers rapid entry to synthetically valuable biaryl aldehydes from abundant anisoles. The synthetic utility of this strategy has been demonstrated in sequential processes to construct complex biaryls, exploiting the orthogonal selectivity of C-O bond activation.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Jun Zhu, Rui Zhang, Guangbin Dong
Summary: A rare reversible C-C single-bond metathesis reaction catalyzed by ruthenium was reported, enabling the synthesis of biaryl compounds under redox-neutral and pH-neutral conditions. The reaction mode involves unexpected 18-electron closed-shell intermediates and is expected to inspire the development of more general C-C single-bond metathesis and orthogonal cross-coupling reactions.
Article
Chemistry, Multidisciplinary
Marc Magre, Josep Cornella
Summary: A bi-catalyzed synthesis of sulfonyl fluorides from (hetero)aryl boronic acids is demonstrated using organobismuth(III) catalysts, resulting in excellent yields and wide functional group tolerance. The catalytic cycle involves various organometallic steps without changing the oxidation state, forming a structurally unique bismuth sulfinate complex.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Weiqi Liu, Xinghao Jin, Dawei Ma
Summary: The requirement of higher reaction temperatures for SNAr reaction between thiols and less reactive electron-poor aryl halides has led to the development of metal- and photo-catalyzed methods. In this study, the SNAr reaction between thiols and most electron-poor aryl halides was found to occur at RT-60°C using K2CO3 and DMAc. Additionally, two oxalic diamide ligands were identified to enable Cu-catalyzed coupling reactions with low catalytic loadings for unreactive (hetero)aryl halides, offering a promising approach for preparing (hetero)aryl thioethers.
Article
Chemistry, Organic
Nathaniel S. Greenwood, Jonathan A. Ellman
Summary: This study reports the sulfur-(hetero)arylation of sulfenamides with commercially abundant (hetero)aryl iodides using inexpensive copper(I) iodide as the catalyst. The reaction inputs include both aryl and alkyl sulfenamides and highly sterically hindered aryl and 5- and 6-membered ring heteroaryl iodides. The study also discloses the (hetero)arylation of S-methyl sulfenamides, including complex aryl iodides, and the Smiles rearrangement of electron-deficient S-heteroaryl sulfilimines.
Article
Chemistry, Organic
Chuntao Zhong, Mengna Liu, Xianchao Qiu, Hao Wei, Benqiang Cui, Yanhui Shi, Changsheng Cao
Summary: A nickel-catalyzed cross-coupling reaction between aryl methyl sulfides and aryl bromides has been developed to efficiently access biaryls. The method has a wide scope of substrates and is scalable, with commercially available aryl bromides being used without the need for preparation of organometallic reagents. This reaction has high application value.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jun Zhu, Yibin Xue, Rui Zhang, Benjamin L. Ratchford, Guangbin Dong
Summary: This article describes a catalytic method for activating unstrained and nonpolar C-C bonds, using removable directing groups to aid in the hydrogenolysis of unstrained C(aryl)-C(alkyl) bonds in 2,2'-methylenediphenols. The method yields high amounts of monophenol products and is tolerant of a wide range of functional groups. Additionally, the reaction is scalable and the catalyst loading can be reduced to as low as 0.5 mol %. The method also proves effective in cleaving C(aryl)-C(alkyl) linkages in both phenolic resins and commercial novolacs resins. Experimental and computational mechanistic studies show that the transformation occurs through a directed C(aryl)-C(alkyl) oxidative addition pathway, with C-H activation being a competitive but reversible off-cycle reaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Amy C. Dodds, Andrew Sutherland
Summary: A mild and regioselective method for the preparation of unsymmetrical biaryl sulfides using iron(III) catalysis was described. The method was applicable for late-stage thiolation of tyrosine and tryptophan derivatives, and was used for the synthesis of pharmaceutically relevant compounds. Kinetic studies revealed differences in the reaction mechanism depending on the electronic properties of the arenes.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Tristan Delcaillau, Adrian Woenckhaus-Alvarez, Bill Morandi
Summary: A nickel-catalyzed cyanation method using Zn(CN)(2) as the cyanide source has been developed for the functionalization of aryl thioethers, involving both C-S bond activation and C-C bond formation. The combination of ligand dcype and base KOAc is crucial for the efficiency of this transformation. The scalability, low catalyst and reagent loadings, and high functional group tolerance make this reaction useful for late-stage derivatization and polymer recycling in organic chemistry.
Article
Chemistry, Multidisciplinary
Daniel G. Shlian, Erika Amemiya, Gerard Parkin
Summary: The reactions of bis(2-pyridylthio)methane with Me2Zn and Zn[N(SiMe3)(2)](2) produce [Bptm]ZnMe and [Bptm]ZnN(SiMe3)(2), which can be used to synthesize various [Bptm]ZnX derivatives. Among them, [Bptm]ZnH serves as a catalyst for the reduction of CO2 and other carbonyl compounds through hydrosilylation and hydroboration reactions.
CHEMICAL COMMUNICATIONS
(2022)
Review
Chemistry, Multidisciplinary
Robin N. Perutz, Sylviane Sabo-Etienne, Andrew S. Weller
Summary: This article introduces the concept of sigma-CAM and a new approach to reaction mechanisms. It focuses on the characteristics and dynamic rearrangements of sigma-bond complexes, providing examples of the sigma-CAM mechanism supported by experimental and computational evidence. The authors also critically compare alternative mechanisms for metathesis of metal-element bonds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Laurence R. Doyle, Emily A. Thompson, Arron L. Burnage, Adrian C. Whitwood, Huw T. Jenkins, Stuart A. Macgregor, Andrew S. Weller
Summary: The study found that the [S-BAr4F](-) anion enhances the stability of the sigma-alkane complex [Rh(Cy2PCH2CH2PCy2)(norbornane)][S-BAr4F] both thermally and when suspended in pentane. Furthermore, the increased stability of [S-BAr4F](-) salts is mainly attributed to enhanced non-covalent interactions in the lattice.
DALTON TRANSACTIONS
(2022)
Review
Chemistry, Organic
Richa Gupta, Rowan D. Young
Summary: Halodefluorination of alkyl fluorides using group 13 metal halides is a well-known reaction that has undergone significant developments in recent years, including the use of various metal halide sources, development of catalytic processes, and selective halodefluorination in polyfluorocarbons.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Multidisciplinary
Shivashankar Khanapur, Kenneth Lye, Dipendu Mandal, Xin Jie Wee, Edward G. Robins, Rowan D. Young
Summary: We present a general method for labeling both CF3 and CF2H groups in various chemical settings. The method provides good radiochemical yields and molar activities, and is applicable to biologically relevant compounds. The use of target compounds as starting materials and the simplicity of the method make it attractive for drug and radiotracer development.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
James J. J. Race, Alex Heyam, Matthew A. A. Wiebe, J. Diego-Garcia Hernandez, Charlotte E. E. Ellis, Shixing Lei, Ian Manners, Andrew S. S. Weller
Summary: An amphiphilic block copolymer of polyphos-phinoborane has been synthesized using a mechanism-led strategy and its self-assembly behavior has been studied.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
M. Arif Sajjad, Stuart A. Macgregor, Andrew S. Weller
Summary: Non-covalent interactions surrounding cationic Rh s-alkane complexes in crystal structures were analyzed using QTAIM and IGMH approaches. Both structures showed the cations residing in an octahedral array of [BAr4F](-) anions, with the [1-NBA](+) cation system exhibiting more C-HF contacts to the anions. QTAIM and IGMH analyses revealed the strongest atom-atom non-covalent interactions between the cation and anion. The IGMH approach highlighted the directionality of C-HF contacts and the significance of C-Hπ interactions.
FARADAY DISCUSSIONS
(2023)
Article
Chemistry, Multidisciplinary
Tobias Kramer, F. Mark Chadwick, Stuart A. Macgregor, Andrew S. Weller
Summary: This study uses density functional theory calculations to model the selective exo-H/D exchange in a Rh sigma-alkane complex. The results show that exo-H/D exchange is kinetically more accessible than endo-H/D exchange, and the solid-state environment significantly affects the calculated energetics.
HELVETICA CHIMICA ACTA
(2023)
Article
Chemistry, Inorganic & Nuclear
Clarence Tan, Hendrik Tinnermann, Vanessa Wee, Shaun Tan, Simon Sung, Qingyang Wang, Rowan D. Young
Summary: The reaction of alkynes with PC carbene P complex 1 leads to the formation of 773-benzo-A.5-phosphinine rhodium complexes 2. By reacting two equivalents of 1 with diynes, bimetallic 773-benzo-A.5-phosphinine rhodium complexes 3 can be easily accessed. Compounds 2a-c,e and 3a-c were synthesized and characterized, and their performance as catalysts in the hydrosilylation of alkynes was tested. Bimetallic complexes 3a-c showed enhanced activity compared to monometallic and monocationic analogues 2d, with improved yields and reaction rates.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Matthew R. Gyton, Cameron G. Royle, Simon K. Beaumont, Simon B. Duckett, Andrew S. Weller
Summary: The heterogeneous solid-gas reactions of crystals of [Rh(L-2)(propene)][BAr4F] with H-2 and different alkenes and alkynes were investigated using gas-phase NMR spectroscopy. The study provides insights into catalytic pairwise para-H-2 transfer, molecular-level changes in the crystalline catalyst, and the production of high-quality gas-phase spectra. The results reveal the formation of dimeric [Rh(L-2)(H)(mu-H)](2)[BAr4F](2) upon reaction with H-2 and the conversion of NMR silent para-H-2 to NMR active ortho isomer. The hydrogenation of propene and other alkenes and alkynes showed high levels of initial polarization and strong PHIP effects.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Daniel Csokas, Richa Gupta, Pragati K. Prasad, Kelvin K. K. Goh, Rowan D. Young
Summary: Aluminum acts as an independent halodefluorination reagent in the reaction, where a heavier halogen replaces aliphatic fluorine. The role of catalytic aluminum halide and organyl alane reagents is not fully understood. Computational and experimental results suggest that the observed reactivity trends between different halide reagents can be attributed to relative barriers in halide delivery to the organic fragment, which is the rate-limiting step in both aluminum halide- and B(C6F5)3-catalyzed pathways.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Mathew J. Cross, Claire N. Brodie, Dana G. Crivoi, Joe C. Goodall, David E. Ryan, Antonio J. Martinez-Martinez, Alice Johnson, Andrew S. Weller
Summary: The formation of nanoparticles during the selective production of polyaminoborane [H2BNMeH](n) using [Rh(L1)(η(2):η(2)-H3B center dot NRH2)] [OTf] and [Rh(L1)(NMeH2)][OTf] as catalysts is observed, but there is ambiguity as to whether the catalysis is solely nanoparticle promoted or if there is a molecular homogeneous component.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Joe C. Goodall, M. Arif Sajjad, Emily A. Thompson, Samuel J. Page, Adam M. Kerrigan, Huw T. Jenkins, Jason M. Lynam, Stuart A. Macgregor, Andrew S. Weller
Summary: The group 7 complexes [M(& kappa;(3)-2,6-(R2PO)(2)C5H3N)(CO)(2)L][BAr4F] [M = Mn, R = Pr-i, L = THF; M = Re, R = Bu-t, L = vacant site] undergo solid-gas reactivity with CO in the crystals to form THF substitution products or CO addition products. The [BAr4F] anions show large, local, adaptive changes for M = Mn, while the changes are smaller and remote to the site of reactivity for M = Re.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Oliver P. E. Townrow, Andrew S. Weller, Jose M. Goicoechea
Summary: Using Zintl clusters as starting materials, eleven- and twelve-vertex homo- and hetero-multimetallic clusters were synthesized through reactions and stepwise methods. The proposed mechanism based on density functional theory calculations explains the formation of these clusters. These studies provide important insights into the assembly mechanisms of Zintl clusters in solution.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Zhi Hao Toh, Hendrik Tinnermann, Dinh Cao Huan Do, Han Vinh Huynh, Tobias Kramer, Rowan D. Young
Summary: We isolated and characterized the gold(i)-iron(0) adducts and found that the gold-iron interaction is predominantly a sigma-donation from iron to gold. The Pr-i(2)-bimy carbenic C-13 NMR signal can be used to gauge the relative donor strength of Fe(0) donors.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Oliver P. E. Townrow, Simon B. Duckett, Andrew S. Weller, Jose M. Goicoechea
Summary: The ligand exchange reactions lead to clusters with coordinatively unsaturated rhodium(i) centers, which can act as catalysts for H/D exchange and alkene isomerisation. Protonation of these clusters results in cationic rhodium-hydride complexes, showing their activity in both H-H and C-H bond activation processes.
Article
Chemistry, Multidisciplinary
Alexander M. Prophet, Kritanjan Polley, Gary J. Van Berkel, David T. Limmer, Kevin R. Wilson
Summary: The oxidation kinetics of iodide by ozone at the air-water interface is studied in single microdroplets. Molecular simulations and kinetic modeling are used to understand the underlying multiphase mechanism.
Article
Chemistry, Multidisciplinary
Rong Zhang, Jiajing Lan, Fei Wang, Shumei Chen, Jian Zhang
Summary: By utilizing 1,1'-ferrocene dicarboxylic acid as a chelating and surface protection ligand, we have synthesized multi-nuclear indium oxide clusters with varying nuclear sizes, including heptanuclear and thirteen-nuclear clusters. These clusters possess labile coordination sites, allowing for structural modification and self-assembly, resulting in the formation of various cluster structures.
Article
Chemistry, Multidisciplinary
Hui Wang, Hui Liu, Mingsen Wang, Jiaheng Hou, Yongjun Li, Yuancheng Wang, Yingjie Zhao
Summary: Two supramolecular complexes were prepared using CBs and M1, and their single-crystal structures were analyzed by SCXRD. The unexpected 1:2 self-assembly structure between M1 and CB[8] was discovered for the first time. These complexes exhibit unique photophysical properties and provide valuable information about the structure and photophysical properties of supramolecular complexes.
Article
Chemistry, Multidisciplinary
Chang-Hee Lee, Sookil Park, Sanggil Kim, Ji Young Hyun, Hyun Soo Lee, Injae Shin
Summary: The epidermal growth factor receptor (EGFR) is a cell-surface glycoprotein involved in cell proliferation and tumor development. This study used a fluorescently labeled EGFR to investigate its time-dependent endocytosis in live cells and found that appended glycans affect EGFR internalization. Additionally, the study detected sialic acid residues attached to EGFR on the live cell surface using FRET-based imaging. This research provides valuable insights into the cellular functions of EGFR.
Article
Chemistry, Multidisciplinary
Subhankar Sahu, Lokesh Kumar, Sumita Das, Dipti Gupta, Ruchi Anand
Summary: This study proposes a strategy that combines organic electronics with biosensor scaffolds to create a compact device for monitoring environmental aromatic pollution. By coupling biosensing protein MopR with an organic electrochemical transistor (OECT), a sensor module capable of efficient detection of phenol was designed. Exclusive phenol detection with minimal loss of sensitivity could be achieved in complex pollutant mixtures and real environmental samples.
Review
Chemistry, Multidisciplinary
Changseok Lee, Hyung-Joon Kang, Sungwoo Hong
Summary: The formation of C-N bonds through hydroamination reactions catalyzed by nickel hydrides has been a topic of recent interest. This approach offers a way to efficiently transform a variety of alkene and alkyne substrates into compounds enriched with C-N bonds. The review provides a concise overview of the underlying reaction mechanisms and aims to stimulate further progress in NiH-catalytic techniques and catalyst design.
Article
Chemistry, Multidisciplinary
Yueci Wu, Lu-Lu Sun, Hai-Hao Han, Xiao-Peng He, Weiguo Cao, Tony D. James
Summary: Drug-induced liver injury (DILI) is a common cause of acute liver failure in the USA and Europe, but most cases can be recovered or prevented by discontinuing the offending drug. Recent research has found that peroxynitrite (ONOO-) can be used as a potential indicator for early diagnosis of DILI, and there is an urgent need to establish a method to detect and track peroxynitrite in DILI cases. In this study, a FRET-based nano fluorescent probe CD-N-I was developed, which showed high selectivity and sensitivity in detecting peroxynitrite. The probe successfully detected exogenous peroxynitrite in live cells and endogenous peroxynitrite in APAP-induced liver injury of HepG2 cells.
Article
Chemistry, Multidisciplinary
Dmitry L. Lipilin, Mikhail O. Zubkov, Mikhail D. Kosobokov, Alexander D. Dilman
Summary: This article describes a direct photocatalytic method for the thiolation of unprotected acids, which was previously challenging. By using a thionocarbonate reagent with an N-O bond, the efficient conversion of carboxylic acids to thiols is achieved.
Article
Chemistry, Multidisciplinary
Jason Malenfant, Lucille Kuster, Yohann Gagne, Kouassi Signo, Maxime Denis, Sylvain Canesi, Mathieu Frenette
Summary: Raman microscopy can reveal compound-specific vibrational fingerprints without sample preparation. The combination of efficient theoretical calculations and a user-friendly software can accurately predict peak positions and provide match scores to assist with structure determination.
Article
Chemistry, Multidisciplinary
Jayoh A. Hernandez, Paul S. Micus, Sean Alec Lois Sunga, Luca Mazzei, Stefano Ciurli, Gabriele Meloni
Summary: Essential trace metals play crucial roles in the survival and virulence of bacterial pathogens. Helicobacter pylori requires nickel for colonization and persistence in the stomach, and NixA is an essential nickel transporter in this process. This study characterizes the selectivity and electrogenic nature of NixA-mediated nickel transport.
Article
Chemistry, Multidisciplinary
Tarali Devi, Kuheli Dutta, Jennifer Deutscher, Stefan Mebs, Uwe Kuhlmann, Michael Haumann, Beatrice Cula, Holger Dau, Peter Hildebrandt, Kallol Ray
Summary: This study emphasizes the importance of subtle electronic changes and secondary interactions in the stability of biologically relevant metal-dioxygen intermediates. It also shows that the role of the chloride ligand in stabilizing the Fe-III-(OOBu)-Bu-t moiety can extend to other anions, including the thiolate ligand.
Article
Chemistry, Multidisciplinary
Jacqueline R. Santhouse, Jeremy M. G. Leung, Lillian T. Chong, W. Seth Horne
Summary: By studying the folding kinetics and mechanism of the BdpA sequence, researchers found that altering the backbone connectivity can affect protein folding. This suggests that protein mimetic chains have a significant degree of plasticity in transitioning between unfolded and folded states.
Article
Chemistry, Multidisciplinary
Divanshu Gupta, Ralf Einholz, Holger F. Bettinger
Summary: This study presents the first direct spectroscopic evidence of a cyclic seven-membered iminoborane. Compared to linear amino-iminoboranes, this cyclic iminoborane exhibits weakened bond strength and lower Lewis acidity value. The study suggests that the reduced ring strain of cyclic iminoborane prevents nitrogen fixation but allows facile (2 + 2) cycloaddition reaction with C2H4.
Article
Chemistry, Multidisciplinary
Renny Mathew, Aniruddha Mazumder, Praveen Kumar, Julie Matula, Sharmarke Mohamed, Petr Brazda, Mahesh Hariharan, Brijith Thomas
Summary: This study reveals the packing arrangement of partially disordered nitro-perylenediimide (NO2-PDI) using a synergistic approach that combines 3D ED, ssNMR, and DFT techniques. By overcoming these challenges, this methodology opens up new avenues for material characterization, driving exciting advancements in the field.
