Article
Chemistry, Organic
Wen-Xin Li, Bo-Wen Yang, Xuan Ying, Zhuo-Wen Zhang, Xue-Qiang Chu, Xiaocong Zhou, Mengtao Ma, Zhi-Liang Shen
Summary: The direct cross-coupling of diaryl sulfoxides with aryl bromides via C-S bond cleavage was achieved using nickel(II) as the catalyst, 1,2-bis(diphenylphosphino)ethane (dppe) as the ligand, and magnesium turnings as the reducing metal in THF. This reaction showed a wide range of substrates and could be used for gram-scale synthesis. The one-pot reaction is operationally simple and economically efficient.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Multidisciplinary Sciences
Lara E. Zetzsche, Jessica A. Yazarians, Suman Chakrabarty, Meagan E. Hinze, Lauren A. M. Murray, April L. Lukowski, Leo A. Joyce, Alison R. H. Narayan
Summary: This study demonstrates the use of cytochrome P450 enzymes for biocatalytic cross-coupling reactions, enabling the formation of sterically hindered biaryl bonds through oxidative C-C bond formation. By engineering the substrate and atroposelectivity of the P450 enzyme, a highly efficient and selective process has been developed.
Article
Chemistry, Organic
Ze-Yu Tian, Zeng-Hui Lin, Cheng-Pan Zhang
Summary: A selective formal C-H/C-H cross-coupling of azoles and (hetero)arenes was established using arylsulfonium intermediates under transition-metal catalysis, providing a variety of 2-(hetero)aryl azoles in good to excellent yields. The advantages of this reaction include mild reaction conditions, good functional group tolerance, a wide substrate scope, high regio- and chemoselectivity, one-pot procedures, and late-stage functionalization of complex molecules without the use of oxidants, offering a promising strategy for transition-metal-catalyzed C-H arylation of azoles.
Article
Biochemistry & Molecular Biology
Martina Hurtova, David Biedermann, Zuzana Osifova, Josef Cvacka, Katerina Valentova, Vladimir Kren
Summary: In this study, we utilized the Suzuki-Miyaura cross-coupling reaction to synthesize a library of flavonoid derivatives for biological activity assays. We explored the reactivity of halogenated flavonoids with aryl boronates and boronyl flavonoids. This method enabled the preparation of various flavonoid derivatives substituted at C-8, and was successfully applied to the synthesis of natural compounds and rare C-8 hydroxyflavonoids.
Article
Chemistry, Organic
Che-Ming Hsu, Shao-Chi Lee, Hao-En Tsai, Yong-Ting Tsao, Cheng-Lin Chan, Shinje Minoza, Zong-Nan Tsai, Li-Yun Li, Hsuan-Hung Liao
Summary: In this study, we successfully activated the C-S bond in sp(3)-hybridized thiols by introducing a per-/polyfluoroaryl moiety, enabling the efficient removal of sulfur groups and the generation of aliphatic radicals that can react with aryl halides.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Engineering, Chemical
Laura Adarve-Cardona, Diego Gamba-Sanchez
Summary: In this manuscript, we describe a method for reducing sulfoxides using ethyl vinyl ether/oxalyl chloride. The reaction involves the formation of chlorosulfonium salts, which are highly electrophilic and react with the sulfoxide. The nucleophilic vinyl ether then scavenges the chlorine, resulting in the formation of the corresponding sulfide. This method is suitable for large-scale applications and can be used with highly functionalized sulfoxides. Chromatographic purification is only necessary in special cases, and the final product can usually be obtained by simple evaporation.
Article
Chemistry, Multidisciplinary
Cheng Chen, Minyan Wang, Hongjian Lu, Binlin Zhao, Zhuangzhi Shi
Summary: Alkyl thianthrenium salts have been synthesized as reliable alkylation reagents, which can readily engage in copper-catalyzed Sonogashira and Kumada reactions to build C(sp(3))-C(sp) bonds under mild photochemical conditions. The method demonstrates great functional breadth and compatibility, even with sensitive Cl, Br, and I atoms.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Paul O. Peterson, Matthew Joannou, Eric M. Simmons, Steven R. Wisniewski, Junho Kim, Paul J. Chirik
Summary: The synthesis and characterization of phenoxy(imine) iron(II) alkyl precatalysts for C(sp2)-C(sp3) Suzuki-Miyaura cross-coupling reaction is reported. This method utilizes mild alkoxide bases and nonpolar solvents to achieve high efficiency C(sp2)-C(sp3) bond formation with various aryl boronic esters and alkyl bromides. The study also highlights the compatibility of the precatalysts with base-sensitive functionality and the role of boronate intermediates in transmetalation.
Article
Chemistry, Physical
Antonio J. LaPorte, Yao Shi, Jason E. Hein, Martin D. Burke
Summary: Stereospecific Csp(3) Suzuki-Miyaura cross-coupling simplifies the synthesis of stereochemically complex small molecules, but current methods are not compatible with complex building blocks commonly found in natural products and other complex targets. This study presents a method for embedding the alpha-methyl-beta-hydroxyl motif within stereochemically defined secondary alkyl boronic ester building blocks, allowing for stereospecific cross-coupling. The use of beta-aryloxysilyl groups addresses the decrease in reactivity and side reactions associated with beta-oxygen-containing Csp(3) boronic esters. Mechanistic studies reveal the activation of a dihydroxysiloxaborolate as a transmetalation partner in a stereospecific process that retains configuration.
Article
Chemistry, Organic
Feiyan Yang, Chuan Wang
Summary: In this study, we employ polycyclic aryl-activated alkyl ammonium triflates as the electrophilic aryl-activated alkylating agent in the nickel-catalyzed hydroxyl- or sulfonamide-directed cross-electrophile coupling reaction with phenyl benzoates, resulting in the synthesis of diverse aryl ketones under mild conditions.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Jacob R. Ludwig, Eric M. Simmons, Steven R. Wisniewski, Paul J. Chirik
Summary: A cobalt-catalyzed method for the C(sp(2))-C(sp(3)) Suzuki-Miyaura cross coupling of aryl boronic esters and alkyl bromides was developed, with cobalt-ligand combinations being assessed through high-throughput experimentation. The use of cobalt(II) sources with trans-N,N'-dimethylcyclohexane-1,2-diamine (DMCyDA, L-1) resulted in optimal yield and selectivity. The transformation allowed for diverse steric and electronic properties on the aryl boronate nucleophile as well as various levels of branching and synthetically valuable functionality on the electrophile, with radical trap experiments supporting the formation of electrophile-derived radicals during catalysis.
Article
Chemistry, Organic
Qiang Wang, Shuaijie Wu, Yi-Dong Wang, Jing Sun, Ying Han, Chao-Guo Yan, Lei Wang
Summary: Here, a new and efficient strategy for the synthesis of alkenyl sulfoxides is reported. The method involves the transition metal-free C-S cross-coupling reaction between sulfenate anions and alkenylsulfonium salts. The in situ generation of sulfenate anions from beta-sulfinyl esters under mild conditions provides an effective approach for the synthesis of diverse alkenyl sulfoxides in moderate to good yields.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Physical
L. Reginald Mills, David Gygi, Jacob R. Ludwig, Eric M. Simmons, Steven R. Wisniewski, Junho Kim, Paul J. Chirik
Summary: In this study, efficient precatalysts for the C(sp(2))-C(sp(3)) Suzuki-Miyaura cross-coupling reaction between alkyl bromides and neopentylglycol (hetero)arylboronic esters were generated in situ using Cobalt(II) halides in combination with phenoxyimine (FI) ligands. The protocol allowed for efficient C-C bond formation with various nucleophiles and electrophiles. The results also suggested that alkyl radicals play an important role in the catalytic reaction.
Review
Chemistry, Physical
Brijesh S. Kadu
Summary: Palladium has been widely used in the Suzuki-Miyaura cross coupling reaction for over 30 years, but it comes with drawbacks such as high cost, tedious work-ups, product contamination, and metal leaching. In recent years, other metals like Ni, Cu, Co, Fe, Rh, and Ru have attracted attention for their potential in SMCR, allowing for the synthesis of industrially important compounds with various functional groups. This review discusses recent advancements in catalysis related to SMCR, providing valuable insights for researchers in designing synthetic protocols for pharmacophores and drug molecules.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)
Article
Chemistry, Multidisciplinary
Aoi Yoshita, Yota Sakakibara, Kei Murakami
Summary: This article presents a method for synthesizing alpha-aryl and alpha-alkynylated alkenylammonium salts through Suzuki-Miyaura and Sonogashira coupling reactions.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2023)
Article
Chemistry, Multidisciplinary
Jack Stewart, Martin Fuchs, Jack Payne, Oliver Driscoll, Gabrielle Kociok-Kohn, Benjamin D. Ward, Sonja Herres-Pawlis, Matthew D. Jones
Summary: Nine new complexes based on thioether appended iminophenolate (ONS) ligands have been synthesized and fully characterized using NMR spectroscopy. The solid-state structures and catalytic performance of these complexes in polymerization and degradation reactions have been investigated.
Article
Chemistry, Inorganic & Nuclear
Ravi Shankar, Priyanka Chauhan, Ekta Jakhar, Archishmati Dubey, Gabriele Kociok-Kohn
Summary: An intensive study on organotin cations with weakly coordinating trifluoromethanesulfonate/arylsulfonate has provided crucial insights into their stability, structural aspects, and catalytic role. The chemistry involving alkanesulfonate ligands remains incomplete due to the presence of strong Sn-O bond. In this study, the scope of diorganostannates, [n-Bu4N][R2Sn(OSO2R1)3] (R = n-Bu, R1 = Me(1), Et(2); R = Ph, R1 = Me(3)), as reactive substrates in the presence of adventitious water was investigated, leading to the formation of [n-Bu2SnOH(OSO2Me)] (4), [n-Bu2Sn(H2O)4][n-Bu4N][OSO2Et]3 center dot H2O (5), and [Ph2Sn(H2O)4][n-Bu4N]2[OSO2Me]4 (6). The crystallographic studies of these compounds reveal their structural identity and the role of alkanesulfonate anions in the formation of supramolecular assemblies.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Andrew J. Straiton, Claire L. McMullin, Gabriele Kociok-Koehn, Catherine L. Lyall, James D. Parish, Andrew L. Johnson
Summary: Analogous to alkoxide ligands, metal boroxide and boryloxy complexes are a lesser studied type of hard anionic O- ligands. A new series of amine-stabilized Li, Sn(II), and Zn boryloxy complexes with electron-rich tetrahedral boron centers were synthesized and characterized. The complexes were characterized using 1D, 2D, and DOSY NMR, and solid-state structures were determined via single-crystal X-ray diffraction. The amine-stabilized boryloxy ligand showed enhanced x-donor ability due to electron donation from the amine functionality into the p-orbital of the boron atom, as evidenced by computational quantum chemical studies.
INORGANIC CHEMISTRY
(2023)
Article
Polymer Science
Craig Hardy, Gabriele Kociok-Kohn, Antoine Buchard
Summary: Introducing sulfur atoms into polymer backbones can utilize abundant chemical industry by-products and adjust polymerization thermodynamics for polymer recycling. By replacing oxygen with sulfur atoms in bio-derived polymers, their properties can be fine-tuned and application scope widened. This study reports the synthesis and characterization of cyclic carbonate and thiocarbonate monomers made from carbohydrate derivative d-glucal, varying the number and position of sulfur atoms in the polymerizable ring. The influence of sulfur on polymer properties such as ring strain, monomer conversion, crystallinity, thermal degradation, and glass transition temperature is examined, providing insights for the design of sulfur-containing renewable polymeric materials in the future.
Article
Chemistry, Inorganic & Nuclear
Devyani Srivastava, Amita Singh, Gabriele Kociok-Kohn, Om Prakash, Abhinav Kumar, Mohd. Muddassir
Summary: This report presents two sulfido-bridged trinuclear Ni(II) clusters and characterizes them using X-ray crystallography. The non-covalent interactions and Ni dot dot dot Ni interactions in these compounds are analyzed using Hirshfeld surface analysis, density functional theory, and quantum theory of atoms-in-molecules.
INORGANICA CHIMICA ACTA
(2023)
Article
Crystallography
Devyani Srivastava, Om Prakash, Gabriele Kociok-Kohn, Abhinav Kumar, Abdullah Alarifi, Naaser A. Y. Abduh, Mohd Afzal, Mohd Muddassir
Summary: Two Ni(II) complexes with distorted square planar geometry and interesting supramolecular structures were synthesized and characterized. The supramolecular frameworks were sustained by C-H...pi and C-H...F interactions. These complexes also exhibited intriguing intramolecular C-H...Ni interactions.
Article
Chemistry, Multidisciplinary
Fernando Cortezon-Tamarit, Kexin Song, Navaratnarajah Kuganathan, Rory L. Arrowsmith, Sara Raquel Mota Merelo de Aguiar, Philip A. Waghorn, Adam Brookfield, Muralidharan Shanmugam, David Collison, Haobo Ge, Gabriele Kociok-Kohn, Charareh Pourzand, Jonathan Robin Dilworth, Sofia Ioana Pascu
Summary: This article primarily focuses on the structural chemistry and metal complex formation of a new family of rigid mono(thiosemicarbazone) ligands. The synthesis of new ligands and their metal complexes was successfully achieved using a microwave-assisted method, which proved to be more efficient than conventional heating. The modification of the ligands with organic linkers opens up possibilities for bioconjugation protocols of these compounds.
Article
Chemistry, Inorganic & Nuclear
Antoine Buchard, Matthew G. Davidson, Gerrit Gobius du Sart, Matthew D. Jones, Gabriele Kociok-Kohn, Strachan N. Mccormick, Paul Mckeown
Summary: We have reported three niobium-based initiators for the catalytic ring-opening polymerization (ROP) of epsilon-caprolactone, exhibiting good activity and molecular weight control. Among them, a monometallic cationic alkoxo-Nb(V) epsilon-caprolactone adduct has been prepared on the gram-scale and characterized, which represents an unprecedented example of a metal complex with an intact lactone monomer and a functional ROP-initiating group simultaneously coordinated at the metal center. At 80 degrees C, all three systems initiate the immortal solution-state ROP of epsilon-caprolactone via a coordination-insertion mechanism, which has been confirmed through experimental studies, and is supported by computational data. Natural bond orbital calculations further indicate that polymerization may necessitate isomerization about the metal center between the alkoxide chain and the coordinated monomer. The observations made in this work are expected to inform mechanistic understanding both of amine tris(phenolate)-supported metal alkoxide ROP initiators, including various highly stereoselective systems for the polymerization of lactides and of coordination-insertion-type ROP protocols more broadly.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Hugh J. Sanderson, Gabriele Kociok-Kohn, Ulrich Hintermair
Summary: The first magnesium pentalenide complexes were synthesized via deprotonative metalation, and their structure and reactivity were studied. The electronic influence of the aryl substituents on the pentalenide core resulted in electrophilic addition at 1,5-positions instead of 1,4-positions.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Jodie L. Hann, Catherine L. Lyall, Gabriele Kociok-Kohn, Simon E. Lewis
Summary: This study presents a method for the synthesis of N-alkoxycarbonyl pyrroles by the condensation of readily available O-substituted carbamates with 2,5-dimethoxytetrahydrofuran. It is demonstrated that N-alkoxycarbonyl protection can impart distinct reactivity to pyrrole in comparison with N-sulfonyl protection.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Polymer Science
Ella F. Clark, Gabriele Kociok-Kohn, Matthew G. Davidson, Antoine Buchard
Summary: In this study, d-xylose 3,5-anyhydrosugar (d-Ox) was used in the ring-opening copolymerisation (ROCOP) with isothiocyanates to form alternating AB-type copolymers with imidothiocarbonate linkages. The use of an Al(iii)-based aminotrisphenolate complex as catalyst allowed the synthesis of thermally robust polymers with high glass-transition temperatures. The reactivity can be tailored by using an Al(iii) porphyrin complex as catalyst, enabling the formation of a non-polymerisable cyclic thionocarbamate byproduct. The polymers exhibited degradation under acidic and basic conditions, as well as photodegradation.
Article
Chemistry, Multidisciplinary
Devyani Srivastava, Amita Singh, Gabriele Kociok-Koehn, Suresh W. Gosavi, Ratna Chauhan, Muthupandian Ashokkumar, Abhinav Kumar, Mohd. Muddassir
Summary: Three new heteroleptic Co(iii) ferrocene dithiocarbamate complexes with dppe as ligand have been synthesized and characterized. Single crystal X-ray diffraction revealed a distorted octahedral geometry around Co(iii) in the complexes. The compounds were used as photo-sensitizers in dye-sensitized solar cells and exhibited good photovoltaic performance.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Chiteri Gautam, Devyani Srivastava, Gabriele Kociok-Kohn, Suresh W. Gosavi, Vinod K. Sharma, Ratna Chauhan, Dattatray J. Late, Abhinav Kumar, Mohd. Muddassir
Summary: Two Schiff base complexes, [CuL2] (Cu-Sal) and [CoL3] (Co-Sal), were synthesized and characterized. Crystal structure analysis showed a square planar geometry around Cu(ii) and various intermolecular non-covalent interactions in Cu-Sal. Both complexes were used as sensitizers in TiO2 based dye sensitized solar cells (DSSCs), and Co-Sal exhibited better photovoltaic performance than Cu-Sal due to improved light absorption and dye loading.
Article
Biochemistry & Molecular Biology
Megan J. Green, Haobo Ge, Stephen E. Flower, Charareh Pourzand, Stanley W. Botchway, Hui-Chen Wang, Navaratnarajah Kuganathan, Gabriele Kociok-Kohn, Meng Li, Suying Xu, Tony D. James, Sofia I. Pascu
Summary: New design and synthetic strategies were developed to generate functional phenyl boronic acid-based fluorescent probes with a 1,8-naphthylimide bright core, and their beta-d-glucan hybrids. These were monitored by MP FLIM for their ability to report changes in their environments in live cells.
RSC CHEMICAL BIOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Devyani Srivastava, Aparna Kushwaha, Gabriele Kociok-Kohn, Suresh W. Gosavi, Ratna Chauhan, Muthupandian Ashokkumar, Abhinav Kumar, Mohd. Muddassir
Summary: Three new nickel complexes were synthesized and used as sensitizers in dye sensitized solar cells (DSSCs). Among the three sensitizers, the DSSC fabricated using p-NiL exhibited the best photovoltaic performance with an efficiency of 3.40%, strong electronic coupling, and enhanced electron injection.
