Article
Chemistry, Multidisciplinary
Garrit Wicker, Rundong Zhou, Roland Schoch, Jan Paradies
Summary: The stereospecific sigmatropic carbon shift of C3 ammonium enolates has been discovered. According to mechanistic, kinetic, and computational experiments, this rearrangement proceeds via the catalytic generation of a transient C3 ammonium enolate by intramolecular aza-Michael addition. The reaction produces tetrahydroquinoline-4-ones with excellent diastereoselectivities and high yields.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Yihong Wang, Claire M. Young, Honglei Liu, Will C. Hartley, Max Wienhold, David B. Cordes, Alexandra M. Z. Slawin, Andrew D. Smith
Summary: This study reports the catalytic generation of C(1)-ammonium enolates from alpha-silyl-alpha-alkyl substituted carboxylic acids using the isothiourea HyperBTM. This desilylative approach allows access to alpha-unsubstituted and alpha-alkyl substituted C(1)-ammonium enolates, which are typically difficult to obtain using traditional methods. The scope and limitations of this process were established in enantioselective [2+2]-cycloaddition processes with perfluoroalkylketones and selective [2+2]-cycloaddition with trifluoromethyl enones.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Jiin Oh, Jihyeon Park, Keepyung Nahm
Summary: A new type of powerful asymmetric phase transfer catalyst was studied, showing high efficiency in the alpha-alkylation of imines of glycine and alanine ester through synthesis and experimental results. The high efficiency was rationalized through DFT calculations proposing skewed conformers of dual quinuclidiniums at TS.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Kathleen L. May, Sanja Resanovic, Maja W. Chojnacka, Krystyna Herasymchuk, Douglas G. Vaughan, Jianfeng Zhu, J. Wilson Quail, Alan J. Lough, Robert A. Gossage
Summary: The study describes the synthesis and characterization of a small library of Co and Cu derivatives (29 examples) incorporating a specific skeleton. Stable Co(II) and Cu(II) complexes were obtained under different conditions, showing redox-induced decomposition behavior. Different molecular properties were elucidated through single crystal X-ray diffraction and molecular modeling. Only one Co complex in the library displayed reversible one-electron redox properties.
INORGANICA CHIMICA ACTA
(2021)
Article
Chemistry, Physical
Chan-Jin Kim, Francesca Ercole, Yi Ju, Shuaijun Pan, Jingqu Chen, Yijiao Qu, John F. Quinn, Frank Caruso
Summary: Metal-phenolic networks (MPNs) formed through coordination bonding between phenolic molecules and metal ions are a promising class of materials for engineering particle systems. A simple and robust approach to incorporate phenolic moieties into polymers has been reported, providing customizable phenolic ligand building blocks for assembling capsules with tailorable properties. The resulting phenolic building blocks can be used to fabricate capsules with controlled shell thickness, permeability, and cell association properties, potentially enabling applications in therapeutic delivery, imaging, separations, and catalysis.
CHEMISTRY OF MATERIALS
(2021)
Review
Biochemical Research Methods
Maria Vittoria Spanedda, Line Bourel-Bonnet
Summary: This review discusses the recent advances in using cyclic anhydrides as pH-sensitive linkers in bioconjugation chemistry and chemical biology. The stability and reactivity of cyclic anhydrides can be tuned by adjusting their structure, making them important in smart delivery systems.
BIOCONJUGATE CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Kathleen L. May, Roxanne Clement, Alan J. Lough, Robert A. Gossage
Summary: This study describes a new iridium complex and its reactivity, such as its reactions with MeI and HSnPh3, as well as its catalytic activity towards CO and C8H16.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2021)
Article
Biochemistry & Molecular Biology
Jude N. Arokianathar, Will C. Hartley, Calum McLaughlin, Mark D. Greenhalgh, Darren Stead, Sean Ng, Alexandra M. Z. Slawin, Andrew D. Smith
Summary: The isothiourea-catalyzed enantioselective 1,6-conjugate addition of para-nitrophenyl esters to 2,6-disubstituted para-quinone methides is reported, with in situ generation of para-nitrophenoxide from initial N-acylation promoting catalyst turnover. A range of para-nitrophenyl ester products can be isolated or derivatized in situ by addition of benzylamine to give amides at up to 99% yield.
Article
Biochemistry & Molecular Biology
Eduard V. Karamov, Viktor F. Larichev, Galina V. Kornilaeva, Irina T. Fedyakina, Ali S. Turgiev, Andrey V. Shibaev, Vyacheslav S. Molchanov, Olga E. Philippova, Alexei R. Khokhlov
Summary: The antiviral activity of a series of cationic surfactants against SARS-CoV-2 was compared, with the findings showing that an increase in the length and number of hydrophobic tails, as well as the presence of a benzene ring in the molecule, can enhance their disinfectant capabilities, with didodecyldimethylammonium bromide being the most efficient.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2022)
Article
Chemistry, Organic
Sara-Cathrin Krieg, Jennifer Grimmer, Annika Maria Pick, Harald Kelm, Martin Breugst, Georg Manolikakes
Summary: An improved approach for the highly stereoselective synthesis of (Z)-2-oxyenamides is presented in this study. The desired products can be easily obtained in just three steps using aminoacetaldehyde dimethyl acetal as a readily available building block. Various acylated and sufonylated oxyenamides have been synthesized using this improved procedure. Mechanistic and theoretical studies have provided a conclusive explanation for the observed stereoselectivities.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Ai-Ping Xing, Zhenpeng Shen, Zhe Zhao, Xinzhe Tian, Yun-Lai Ren
Summary: The readily available CuO combined with K4Fe(CN)(6) was demonstrated to effectively convert various arylacetic acids into aromatic nitriles, with yields ranging from low to high.
CATALYSIS COMMUNICATIONS
(2021)
Article
Chemistry, Applied
Camilla Loro, Roberto Sala, Michele Penso, Francesca Foschi
Summary: A catalytic, easily scalable protocol for the enantioselective synthesis of Tetrasubstituted alpha-aryl-alpha-amino acid derivatives is reported herein, using a biphasic system composed of catalytic DBU in DME and aqueous solutions of Na2CO3. The heterogeneous system promotes the degradative rearrangement of functionalized N-aryl sulphonyl alpha-amino esters into the corresponding tetrasubstituted 2-aryl-2-amino esters under very mild reaction conditions, achieving high enantiomeric ratios (up to 97.5:2.5) and good yields (up to 95%).
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Polymer Science
Matthias Rohmer, Oezguen Ucak, Rahul Fredrick, Wolfgang H. Binder
Summary: This study investigated the synthesis of several short chain poly(Aib) by ring opening polymerization using different chiral amines as initiators and chiral induction agents, resulting in controlled structure, chirality, and formation of the polymers. The findings revealed excellent chiral induction by the initiators and the influence of solvent environment on the formation of poly(amino acids) aggregates, affecting their chiral induction.
Correction
Chemistry, Organic
Bidisha R. Bora, Rashmi Prakash, Sabera Sultana, Sanjib Gogoi
Summary: This study presents a ruthenium(ii)-catalyzed decarbonylative and decarboxylative coupling of isatoic anhydrides with salicylaldehydes, providing access to aryl 2-aminobenzoates.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Sushree Ranjan Sahoo, Debayan Sarkar, Prathap Somu, Subhankar Paul, Peter Lonnecke
Summary: The addition of boron trifluoride etherate to allenic ketones resulted in the isolation of isolated boron difluoride enolates, whose crystal structure has been determined. The migration of (Z)-beta-difluoroboryloxy ether derivatives from C-1 to C-10 has been observed, leading to rearranged phenol derivatives that can be further functionalized into C-2 alkyl-chromenones. Interestingly, the isolated boron enolates show significant anticancer properties.
Article
Chemistry, Organic
Samuel M. Smith, Mark D. Greenhalgh, Taisiia Feoktistova, Daniel M. Walden, James E. Taylor, David B. Cordes, Alexandra M. Z. Slawin, Paul Ha-Yeon Cheong, Andrew D. Smith
Summary: This study reports the full scope and limitations of catalytic acylative kinetic resolution of a range of tertiary heterocyclic alcohols using a commercially available Lewis basic isothiourea catalyst. The protocol is highly effective for the synthesis of enantioenriched compounds and a detailed kinetic analysis of the reaction mechanism has been provided.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Callum Prentice, James Morrison, Andrew D. Smith, Eli Zysman-Colman
Summary: The donor-acceptor thermally activated delayed fluorescent compounds DiKTa and Mes(3)DiKTa were found to have comparable or better product yields than 4CzIPN in a range of photocatalytic reactions. Among them, DiKTa stands out due to its lower cost, making it a valuable addition to any chemist's collection of photocatalysts.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Grant J. Sherborne, Paul Kemmitt, Callum Prentice, Eli Zysman-Colman, Andrew D. Smith, Charlene Fallan
Summary: This study developed a light-mediated cyclisation method for the selective synthesis of tetrahydroquinolines or quinoline derivatives. The method is efficient, atom economical, and tolerant to functional groups, including azaarene-bearing substrates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Yihong Wang, Claire M. M. Young, David B. B. Cordes, Alexandra M. Z. Slawin, Andrew D. D. Smith
Summary: The isothiourea-catalyzed formal [2+ 2] cycloaddition of C(1)-alkyl and C(1)-unsubstituted ammonium enolates with beta- and alpha,beta-substituted trifluoromethylenones has been developed. The reaction exhibited preferential [2 + 2]-cycloaddition over the alternative [4 + 2]-cycloaddition, resulting in beta-lactones with excellent diastereo- and enantioselectivity. The regioselectivity of the reaction was determined by the substituents on both reactants.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
James Harnedy, Hussain A. Maashi, Albara A. M. A. El Gehani, Matthew Burns, Louis C. Morrill
Summary: Here, an electrochemical approach is presented for the deconstructive functionalization of cycloalkanols, utilizing alcohols, carboxylic acids, and N-heterocycles as nucleophiles. The method is demonstrated to work on various cycloalkanol substrates, with different ring sizes and substituents, resulting in useful remotely functionalized ketone products (36 examples). Additionally, the method is scaled up to gram scale using single-pass continuous flow, showing increased productivity compared to batch processing.
Article
Chemistry, Multidisciplinary
Alastair J. Nimmo, Jacqueline Bitai, Claire M. Young, Calum McLaughlin, Alexandra M. Z. Slawin, David B. Cordes, Andrew D. Smith
Summary: This study demonstrates an unusual reversible Michael addition reaction, using an isothiourea as a Lewis base catalyst, which produces stereoselective products. The basicity of the reaction conditions and the reactivity of the catalyst affect the selectivity of the products. By combining the reversible Michael addition with a crystallisation-induced diastereomer transformation, high yields and stereocontrol of the products can be achieved.
Article
Chemistry, Multidisciplinary
Albara A. M. A. El Gehani, Hussain A. Maashi, James Harnedy, Louis C. Morrill
Summary: This review summarises recent advances (2012-present) in electrochemical approaches for generating and utilizing alkoxy radicals. It discusses the application of these radicals in various transformations, including reaction mechanisms and limitations, and highlights future challenges in sustainable synthesis.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Callum Prentice, Alice E. E. Martin, James Morrison, Andrew D. D. Smith, Eli Zysman-Colman
Summary: The key intramolecular [2 + 2] photochemical cycloaddition step in the synthesis of dimethyl cubane-1,4-dicarboxylate is achieved using substoichiometric amounts of benzophenone as a photosensitizer. The reaction proceeds through a Dexter energy transfer process between the triplet excited state of benzophenone and a known cubane precursor diene. The use of the inexpensive and readily available benzophenone as a photosensitizer allows for the use of lower energy light compared to traditional photochemical processes.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Grant J. Sherborne, Coura Diene, Paul Kemmitt, Andrew D. Smith
Summary: The preparation of bridged benzo-[1,5]-oxazocines and benzo-[1,4]-diazepines from simple starting materials was demonstrated. The reaction involves a one-pot condensation/6 pi electrocyclization followed by an intramolecular trapping step to obtain bridged seven- and eight-membered products. The use of specific aldehydes results in stable zwitterionic structures that undergo diastereoselective reduction under hydrogenative conditions. A similar cyclization/hydrogenation pathway with excellent diastereoselectivity was also observed.
Article
Chemistry, Multidisciplinary
Ding Yuan, Alister S. Goodfellow, Kevin Kasten, Zhuan Duan, Tengfei Kang, David B. Cordes, Aidan P. Mckay, Michael Buhl, Gregory R. Boyce, Andrew D. Smith
Summary: This study demonstrates the enantioselective conjugate addition of carbo- and heterocyclic alpha-substituted beta-ketoesters to alpha,beta-unsaturated aryl esters using HyperBTM as a catalyst. Divergent diastereoselectivity is observed depending on the substituents of the beta-ketoesters, but both cyclopentanone-derived and indanone-derived beta-ketoesters generate desired products with high selectivity.
Article
Chemistry, Organic
Miguel A. Valle-Amores, Claudia Feberero, Ana Martin-Somer, Sergio Diaz-Tendero, Andrew D. Smith, Alberto Fraile, Jose Aleman
Summary: In this study, a highly enantioselective organocatalyzed [3 + 2] cycloaddition reaction between furanone derivatives and azomethine ylides was presented. The success of this reaction is attributed to intramolecular hydrogen bond activation and the formation of highly multifunctional bicyclic adducts with five stereogenic centers. The reaction also achieved a highly efficient kinetic resolution of butenolides, leading to the formation of furan-2(5H)-ones and furo[3,4-c]pyrrolidinones with high enantioselectivities. Quantum chemistry calculations revealed the crucial role of hydrogen bonding in promoting facial discrimination and achieving a highly selective kinetic resolution.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Callum Prentice, James Morrison, Eli Zysman-Colman, Andrew D. Smith
Summary: The recently reported organic multi-resonant thermally activated delayed fluorescence (MR-TADF) photocatalyst DiKTa enables the modular synthesis of 1,4-diketones under mild and metal-free conditions. The reaction proceeds via a three-component relay process in the presence of an N-heterocyclic carbene (NHC) organocatalyst.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Alex C. Seastram, Mishra Deepak Hareram, Thomas M. B. Knight, Louis C. Morrill
Summary: An electrochemical method for the azidocyanation of alkenes via 1,4-nitrile migration has been developed. The method is applicable to various alkene containing cyanohydrins and provides access to a broad range of synthetically useful 1,2-azidonitriles. The methodology has also been extended to alkene sulfonylcyanation and the synthesis of a trifunctionalized hexanenitrile.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Jerson E. Lapetaje, Claire M. Young, Chang Shu, Andrew D. Smith
Summary: The isothiourea-catalyzed formal enantioselective conjugate addition of 2-hydroxybenzophenone imine derivatives to alpha,beta-unsaturated para-nitrophenyl esters has been developed, producing a range of beta-imino ester and amide derivatives in moderate to good isolated yields with excellent enantioselectivity. Electron-withdrawing substituents within the alpha,beta-unsaturated ester component are required for good product yield.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Roberto del Rio-Rodriguez, Matthew T. Westwood, Marina Sicignano, Martin Juhl, Jose A. Fernandez-Salas, Jose Aleman, Andrew D. Smith
Summary: This study combines the photocatalytic generation of alpha-amino radicals with chiral isothiourea derived alpha,beta-unsaturated acyl ammonium intermediates. The reaction proceeds via a [3+2] radical-polar crossover mechanism to generate gamma-lactams with good yields and enantioselectivities. The enantioselective radical conjugate addition was carried out under batch and flow conditions.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Faiza Diaba, Gisela Trenchs
Summary: The first violet light-mediated synthesis of gamma- and delta-lactams from N-alkenyl trichloroacetamides is reported in this paper. The reactions are conducted in tetrahydrofuran or 2-methyltetrahydrofuran as the sole solvent without catalysts or additives, under non-anhydrous conditions in an air atmosphere where the solvent serves as the radical initiator.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Feroze Hussain, Sajjad Ahmed, Ashiq Hussain Padder, Qazi Naveed Ahmed
Summary: This study reports a novel and efficient one-pot synthesis method for mixed phosphorotrithioates, which does not require supplementary additives and shows broad applicability.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Hyunjin Oh, Ikyon Kim
Summary: A new 1,2,4-triazole-pyrrolo[1,2-a]pyrazine hybrid system, 6-acylpyrrolo[1,2-a][1,2,4]triazolo[5,1-c]pyrazine, was synthesized using a catalyst-free method. This method involved sequential exposure of pyrrole-2-carbonitrile-derived substrates to DMF-DMA and acyl hydrazide, resulting in the formation of acylated pyrazine and 1,2,4-triazole rings, enabling the installation of various substituents at specific positions on the core skeleton.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Ming Yan, Si-fan Wang, Yong-po Zhang, Jin-zhong Zhao, Zhuo Tang, Guang-xun Li
Summary: Here we developed an efficient photocatalytic approach for the convenient preparation of sulfinamides. The reaction allows for the gram-scale preparation of sulfinamides and the one-pot synthesis of various sulfonyl amides.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Farzaneh Bandehali-Naeini, Zahra Tanbakouchian, Noushin Farajinia-Lehi, Nicolas Mayer, Morteza Shiri, Martin Breugst
Summary: Two tandem catalytic systems were developed for the synthesis of novel 3,4-disubstituted maleimides using the same Ugi adducts. Different maleimide structures can be synthesized using either Pd or Cu catalysis.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Tanya Raghava, Anjan Chattopadhyay, Subhadeep Banerjee, Nivedita Sarkar
Summary: Amine substitution of two ortho fluorine atoms of tetrafluoroterephthalonitrile through SNAr chemistry is easily achievable. But further fluorine substitution is only possible under forcing conditions, yielding valuable fluorophores for bioimaging.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Review
Chemistry, Organic
Anju Chadha, Santosh Kumar Padhi, Selvaraj Stella, Sowmyalakshmi Venkataraman, Thangavelu Saravanan
Summary: Alcohol dehydrogenases are enzymes that use cofactors for oxidation or reduction reactions of alcohols or carbonyl compounds. They are utilized in green chemistry and have applications in the production of pharmaceuticals. Recombinant enzymes have solved the challenge of producing purified enzymes in large quantities. Engineered alcohol dehydrogenases have been used in asymmetric synthesis in industry. Various methods have been established for regenerating expensive cofactors to make the enzymatic process more efficient and economically viable.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
