Article
Chemistry, Physical
Jiang Wang, Xin Lin, Pan-Lin Shao, Jingyuan Song, Jialin Wen, Xumu Zhang
Summary: This study presents an Rh/DuanPhos-catalyzed double asymmetric hydrogenation of alpha-iminoketones for accessing chiral vicinal amino alcohols. The methodology offers advantages such as one-pot operation, high efficiency, operational simplicity, limited waste, broad reaction scope, and high yields and stereoselectivities. Furthermore, the mechanism of the transformation was revealed to be a stepwise reaction by isolating and analyzing reaction intermediates.
Article
Biochemistry & Molecular Biology
Mateusz Matwiejuk, Hanna Mysliwiec, Bartlomiej Lukaszuk, Marta Lewoc, Hend Malla, Piotr Mysliwiec, Jacek Dadan, Adrian Chabowski, Iwona Flisiak
Summary: Psoriasis is a complex chronic immunologically mediated disease that affects the skin, nails, and joints. Abnormal levels of sphingolipids significantly differ between psoriatic skin and healthy skin, suggesting their potential role in the pathogenesis of psoriasis.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Multidisciplinary
Guangying Tan, Fritz Paulus, Angel Renteria-Gomez, Remy F. Lalisse, Constantin G. Daniliuc, Osvaldo Gutierrez, Frank Glorius
Summary: Radical addition reactions of olefins are widely used in organic synthesis, but mainly limited to polymerization or 1,2-difunctionalization. This study presents an unprecedented radical relay 1,4-oxyimination of two electronically differentiated olefins using a class of bifunctional oxime carbonate reagents through an energy transfer strategy. The reaction is highly selective and diverse, providing rapid access to valuable products.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
He Huang, Tristan H. Lambert
Summary: A method for the regiodivergent aminooxygenation of aryl olefins under electrophotocatalytic conditions is described, which utilizes a trisaminocyclopropenium ion catalyst and visible light irradiation to convert aryl olefins to oxazoline products with high selectivity. By choosing between water and urethane as reagents, different derivatives of 2-amino-1-ol or 1-amino-2-ol can be synthesized from the same substrate.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Minghui Zhu, Qinglong Zhang, Weiwei Zi
Summary: The study presents a dual-metal catalyzed diastereodivergent coupling method for the synthesis of beta-amino alcohols with multiple stereoisomers, enabling the concise preparation of natural products such as mycestericins F and G.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Emily M. Mumford, Brett N. Hemric, Scott E. Denmark
Summary: This study reports a method for the chemo-, regio-, diastereo-, and enantioselective oxyamination of alkenes using selenium(II/IV) catalysis with a chiral diselenide catalyst. The reaction demonstrates good yields and excellent enantio- and diastereoselectivity for a variety of alkenes and different functional groups. The use of N-tosylamides to generate oxazoline products allows for the assembly of chiral ligands and various protected amino alcohols in an expedited manner.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Cheng Sheng, Zheng Ling, Junzhe Xiao, Kai Yang, Xie Fang, Shengming Ma, Wanbin Zhang
Summary: In this study, enantio- and diastereoselective α-additions of 1-alkynyl ketimines with dual-copper-catalysis were successfully achieved under mild conditions, leading to the synthesis of chiral tetrasubstituted α-amino allenoates bearing a vicinal all-carbon quaternary stereocenter in high yields (up to 99% yield) with excellent enantioselectivities (up to 99% ee) and diastereoselectivities (up to >20:1 dr). The stereodivergent synthesis of the products was realized by the asymmetric α-addition reaction and the Grignard reagent promoted epimerization. Importantly, the reaction could be smoothly scaled up and applied to introduce chiral tetrasubstituted allenyl moieties into bioactive molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Food Science & Technology
Didier Tardieu, Maria Matard-Mann, Pi Nyvall Collen, Philippe Guerre
Summary: The study analyzed the effects of FB on hepatic and plasma sphingolipidome in chickens, showing that alterations in sphingolipids can lead to toxic manifestations and can potentially serve as a biomarker of exposure to FB.
Article
Chemistry, Organic
Lei Zhang, Chengyu Liu, Maolin Sun, Chaoming Liang, Liming Cao, Xiantong Yao, Yueyue Ma, Ruihua Cheng, Jinxing Ye
Summary: An iridium catalytic system using a ferrocene-based phosphine ligand with a modular and tunable unsymmetrical vicinal diamine scaffold was developed for the asymmetric hydrogenation of aryl ketones. This method provided a powerful tool for the enantioselective synthesis of diverse chiral alcohols, exhibiting excellent reactivity and enantioselectivity (yield up to 99%, ee up to 99%, and turnover number up to 50,000). The substituents and chirality of unsymmetrical diamines in the ligands played a crucial role in achieving satisfactory results.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Yu Li, Na Hu, Zefei Xu, Yunfeng Cui, Jinhui Feng, Peiyuan Yao, Qiaqing Wu, Dunming Zhu, Yanhe Ma
Summary: The enzymatic asymmetric reductive amination process can be used to convert simple aldehydes and amines into chiral N-substituted 1,2-amino alcohols, providing an environmentally friendly and economical method.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Mingkang Zhou, Yaodong Lin, Xiao-Xuan Chen, Guangqing Xu, Lung Wa Chung, Wenjun Tang
Summary: We report the chiral diboron-templated asymmetric homocoupling of aryl alkyl ketimines, leading to the formation of chiral vicinal tetrasubstituted diamines with high enantioselectivities and good to high yields. This powerful and efficient reaction is achieved by rational design and engineering of chiral diborons, which participate in a [3,3]-sigmatropic rearrangement. DFT studies reveal that different conformational assembling strategies of chiral diborons ensure the excellent enantioselectivity in the tight concerted transition states.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Samantha L. Gargaro, Raphael K. Klake, Joshua D. Sieber
Summary: Here, we describe the development of a Cu-catalyzed enantioselective borylative aminoallylation reaction using a N-substituted alleneto access boryl-substituted 1,2-aminoalcohol synthons for generating chiral heteroatom-rich organic compounds. The reaction provides easy access to various substitution patterns of chiral 1,2-aminoalcohol products with high diastereo- and enantioselectivity from readily available starting materials.
Article
Chemistry, Organic
Someshwar Nagamalla, Debobrata Paul, Joel T. Mague, Shyam Sathyamoorthi
Summary: We present a unique strategy for the synthesis of vicinal amino alcohols through ring opening of aziridines with pendant silanols, which is compatible with a range of substrates. This method requires mild activation of the aziridine and tolerates various N-substituents. It has been successfully applied in the facile preparation of natural products and analogues.
Article
Chemistry, Organic
Hung-Che Chen, Chi-Yun Liu, Venkatachalam Angamuthu, Wei-Chen Chen, Chi-Sheng Wen, Duen-Ren Hou
Summary: A general method for synthesizing optically active, primary, secondary, and tertiary organofluorides was developed using the chiral pool synthesis strategy. Diastereomerically pure 2-oxazolidinone-fused aziridines, generated from the skeleton of arabinose, underwent ring opening with a fluoride anion, leading to polyoxygenated organofluorides. These compounds served as useful precursors for various fluorinated compounds, including fluorinated amino acids.
Article
Chemistry, Multidisciplinary
Christopher J. J. Hall, William R. F. Goundry, Timothy J. Donohoe
Summary: Enantiopure 1,2-amino alcohols derived from abundant amino acids were used in C-C bond-forming hydrogen-borrowing alkylation reactions for the first time. The use of Ph*COMe aryl ketone facilitated the reactions, preventing racemisation of the amine stereocentre. The Ph* and trityl groups could be easily cleaved in one pot to give GABA products without further purification, allowing the two steps to be performed in sequence without isolation of the hydrogen-borrowing intermediate, eliminating the need for column chromatography.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
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, Organic
Yusra Abdelhamid, Kevin Kasten, Joanne Dunne, Will C. Hartley, Claire M. Young, David B. Cordes, Alexandra M. Z. Slawin, Sean Ng, Andrew D. Smith
Summary: This study reports a method for enantioselective [2 + 2] cycloaddition of C(1) ammonium enolates generated catalytically using the isothiourea HyperBTM with N-alkyl isatins, which leads to the formation of spirocyclic beta-lactones. In situ ring opening with an amine nucleophile generates isolable highly enantioenriched products with a diastereomeric ratio of up to 92:8 and an enantiomeric ratio of > 99:1.
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, Organic
Gregory R. Boyce, Stefania F. Musolino, Jianing Yang, Andrew D. Smith, James E. Taylor
Summary: This study demonstrates the racemization of enantiomerically pure alcohols using 2-carboxyphenylboronic acid and oxalic acid as catalysts in the presence of 2-butanone as a solvent. The process involves reversible Br??nsted acid-catalyzed C???O bond cleavage and the formation of an achiral carbocation intermediate.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Multidisciplinary Sciences
Kissa W. Mwamwitwa, Adam M. Fimbo, Elias M. Bukundi, Alex F. Nkayamba, Deus Buma, Eva P. Muro, Betty A. Maganda, Danstan H. Shewiyo, Morven C. Shearer, Andrew D. Smith, Eliangiringa A. Kaale
Summary: Under-reporting of adverse drug events (ADEs) is a challenge in developing countries, including Tanzania. This study introduced and evaluated the effectiveness of a 'structured stimulated spontaneous safety monitoring' (SSSSM) program, which significantly increased the reporting rate of ADEs and detected signals from various types of medicines.
SCIENTIFIC REPORTS
(2022)
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, Multidisciplinary
Zhuan Duan, Claire M. M. Young, Jiayun Zhu, Alexandra M. Z. Slawin, AnnMarie C. C. O'Donoghue, Andrew D. D. Smith
Summary: This study investigates the effect of NHC and heteroaromatic aldehyde structure on the reaction rate and equilibrium constants. The results show that structural variations significantly affect the kinetic parameters of adduct formation, decay to starting materials, and onward reaction to BI. The study also describes the isolation and characterization of tetrahedral adducts formed during the addition of N-aryl triazolium derived NHCs into heteroaromatic aldehydes.
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, 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, 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
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, 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)
