Article
Chemistry, Organic
Yu-Wen Liu, Ling-Jun Li, Hui Xu, Hui-Xiong Dai
Summary: In this study, we report the synthesis of 1,3-enynes through palladium-catalyzed cross-coupling between enone derivatives and alkynylsilanes. The use of an appropriate pyridine-oxazoline ligand is crucial for achieving C-C cleavage and high E/Z stereoselectivity. This method demonstrates broad substrate scope, wide functional-group tolerance, and moderate-to-good yields. Furthermore, the late-stage diversification of natural product beta-ionone showcases the synthetic utility of this protocol.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Shujun Cao, Huaigui Li, Xinjie Teng, Huaxing Si, Rongshun Chen, Yingguang Zhu
Summary: A domino cyclization of oxime esters and imines has been achieved by dual photoredox/copper catalysis, producing a variety of structurally diverse fully substituted dihydropyrimidines with high molecular complexity and functional group diversity.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Applied
Nengneng Zhou, Qiankun Xu, Ziqin Xia, Fangli Zhao, Lei Wang, Man Zhang
Summary: A copper-catalyzed multicomponent oxysulfonylation of alkenes with cyclobutanone oxime esters and hydroxamic acids via the insertion of sulfur dioxide has been developed. This reaction provides a direct approach to β-amidoxy sulfones in 35-90% yields using K2S2O5 as the sulfur dioxide surrogate and the in situ generated amidoxyl radical as radical interceptor. Mechanistic studies suggest the involvement of a radical-radical coupling reaction between the alkyl radical and amidoxyl radical.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Physical
Nikita Kvasovs, Valeriia Iziumchenko, Vitalii Palchykov, Vladimir Gevorgyan
Summary: This method utilizes visible light-induced generation of nucleophilic hybrid alkyl Pd radical intermediates to achieve efficient atom economical C-C bond construction of alkyl-substituted oximes, allowing a broad range of primary, secondary, and tertiary alkyl bromides and iodides, as well as a range of different formaldoximes, to efficiently undergo this transformation.
Article
Chemistry, Multidisciplinary
Xue-Gong Jia, Qi-Wei Yao, Xing-Zhong Shu
Summary: This study presents a new method for the preparation of enantioenriched heterocycles through N-cyclization-alkylation reaction, addressing a long-standing challenge in the synthetic community and achieving highly enantioenriched pyrrolines under mild conditions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Chenpeng Gao, Christopher A. Wilhelmsen, James P. Morken
Summary: Palladium-catalyzed conjunctive cross-coupling can be achieved using chiral phosphine-oxazoline based ligand structures. This reaction specifically works on Grignard-based boron ate complexes and does not require halide-scavenging additives used in other catalyst systems.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Chenpeng Gao, Christopher A. Wilhelmsen, James P. Morken
Summary: Palladium-catalyzed conjunctive cross-coupling can be achieved using chiral phosphine-oxazoline ligand structures. Notably, the reaction can be performed on Grignard-based boron ate complexes without the need for halide scavenging additives required by other catalyst systems.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Hong-Cheng Shen, Ying Chen, Ying Zhang, He-Ming Jiang, Wen-Qian Zhang, Wen-Ao Li, Mostafa Sayed, Xinhao Zhang, Yun-Dong Wu, Liu-Zhu Gong
Summary: The study demonstrates a nickel-catalyzed enantioselective desymmetrizing aza-Heck cyclization, utilizing a pentafluorobenzoyl leaving group and chiral pybox ligand, with a competitive E2-like pathway and beta-H elimination at the enantioselectivity determining step.
Article
Chemistry, Organic
Zheng-Hai Wang, Dong-Hui Wang
Summary: A Cu-catalyzed straightforward synthesis of benzoxazoles from free phenols and cyclic oxime esters is reported, with moderate to good yields under mild reaction conditions. Large-scale syntheses of Ezutromid and Flunoxaprofe are demonstrated in one or two steps. The proposed catalytic mechanism involves Cu-catalyzed amination via inner-sphere electron transfer and consequent annulation.
Article
Chemistry, Organic
Ming Li, Cui-Tian Wang, Qiao-Fei Bao, Yi-Feng Qiu, Wan-Xu Wei, Xue-Song Li, Yu-Zhao Wang, Zhe Zhang, Jin-Lin Wang, Yong-Min Liang
Summary: The copper-catalyzed radical cross-coupling of oxime esters and activated alkenes successfully produced cyanoalkylsulfonylated oxindoles and cyanoalkyl amides through an aryl migration strategy, with unique desulfonylation and sulfone addition processes involved. The transformation demonstrates good functional group applicability, enabling the regioselective control of two different quaternary stereocenters by the substituent group of the nitrogen atom.
Article
Chemistry, Organic
Sufal Paul, Piyush Kumar Verma, Anubhab Kashyap, Rahul Mondal, K. Geetharani
Summary: A new method has been developed for sequentially gem-thioborylating readily available aldehydes through cobalt-catalyzed diboration reaction. The N-heterocyclic carbene (NHC)-cobalt complex serves as a catalyst for the diboration of aldehydes to generate alpha-oxyl boronic esters, which react with lithium thiolates to form a tetracoordinate boronate species undergoing 1,2-metalate rearrangement in the presence of trifluoroacetic anhydride. The stepwise functionalization of the boryl and thiol moiety of the products enriches the chemical toolbox of diverse organic synthesis.
Article
Chemistry, Physical
Boxiao Tang, Chuan Ding, Min Ou, Yu Liu, Junwei Liu, Yilin Liu
Summary: An efficient acylation/cyclization reaction of 6-acyl phenanthridines with oxime esters using photoredox catalysis has been developed. This strategy enables a facile access to acyl-substituted phenanthridines with good yield and excellent selectivity. The developed method is redox neutral and has broad substrate scope and excellent functional group tolerance.
Article
Chemistry, Organic
Bingbing Dong, Jiansha Lu, Honghao Bao, Yuanyuan Zhang, Yingguo Liu, Yuting Leng
Summary: This copper-catalyzed reaction allows for the radical cross-coupling of cyclobutanone oxime esters with sulfonyl hydrazides, producing a wide range of diversely substituted cyano-containing sulfones. The method is notable for its low-cost catalytic system, lack of toxic reagents, and use of readily accessible starting materials.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Organic
Binlin Zhao, Yukun Zheng, Cheng Chen, Mengning Wang, Mengtao Ma, Zhuangzhi Shi
Summary: A modular, convenient, and practical copper-catalyzed platform has been developed for the preparation of alkene nitriles from cycloketoxime esters through radical-mediated C-C bond cleavage. A broad scope of cycloketoxime esters and some complex substrates derived from natural product derivatives performed well under copper salts, resulting in corresponding ring opening products. Furthermore, etherification, oxidation, and alkynylation of cycloketoxime esters could also be achieved under variable copper-catalyzed conditions.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Shitao Sun, Jinle Hao, Maosheng Cheng, Yongxiang Liu, Bin Lin
Summary: Computational studies provide insight into the regioselectivity of gold(i)-catalyzed intramolecular cycloisomerizations of tryptamine-ynamides. The electrostatic effect is found to be the key factor for alpha-position selectivity, while the dispersion effect is the key factor for beta-position selectivity. These findings guide the understanding of other gold(i)-catalyzed asymmetric alkyne cyclization reactions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Olga O. Sokolova, John F. Bower
Summary: This review summarizes synthetic developments reported from 1987 to 2019 that exploit C-C single bond cleavage of cyclopropylamine-based systems. The synthetic and mechanistic aspects of key methodologies are highlighted, and examples where aminocyclopropanes are exploited as key intermediates in multistep synthesis are also discussed. The review encompasses cases where aminocyclopropanes participate in polar reactions, pericyclic processes, radical-based reactions, and C-C bond activations.
Article
Chemistry, Organic
Nicholas J. Race, Hannah M. Holst, Shelby B. McGuire
Summary: Phenonium ions can be formed through neighboring-group participation of aryl rings, and can undergo regiodivergent openings with chloride nucleophiles. The selectivity of these reactions is controlled by the reagents, allowing for the stereospecific synthesis of complex chiral building blocks from readily accessible epoxide starting materials.
Article
Chemistry, Multidisciplinary
Guilherme A. M. Jardim, Renato L. de Carvalho, Mateus P. Nunes, Luana A. Machado, Leandro D. Almeida, Karim A. Bahou, John F. Bower, Eufranio N. da Silva Junior
Summary: Metal catalyzed C-H functionalization is widely used in organic chemistry for selective functionalization. Understanding the synthesis of transition metal Cp-type catalysts is crucial for modifying the catalyst structure for different applications.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Atanu Modak, Juan Alegre-Requena, Louis de Lescure, Kathryn J. Rynders, Robert S. Paton, Nicholas J. Race
Summary: The ability to manipulate C-C bonds for selective chemical transformations is a challenging and growing area of research. The study reported a formal insertion of diazo compounds into unactivated C-C bonds of benzyl bromide derivatives catalyzed by a simple Lewis acid, resulting in products containing benzylic quaternary centers and alkyl bromides amenable to further derivatization. Computational analysis provided insight into the reaction mechanism, particularly the key selectivity-determining step.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Hannah M. Holst, Jack T. Floreancig, Casey B. Ritts, Nicholas J. Race
Summary: This study demonstrates the synthesis of beta-phenethylamine products through the treatment of unsymmetrical 2,3-disubstituted aziridines with TiCl4, involving the intermediacy of a phenonium ion. Computational analysis provides insight into the reaction mechanism, especially the selectivity of phenonium opening.
Article
Chemistry, Multidisciplinary
Olga O. Sokolova, John F. Bower
Summary: An enantioselective (3+1+2) cycloaddition reaction triggered by carbonylative C-C bond activation of cyclopropanes is achieved using an endo-directing group strategy. This reaction represents a rare example where C-C bond oxidative addition determines the enantiomeric outcome, and it is the first time this has been achieved within the context of a multicomponent reaction design.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Adam D. J. Calow, David Dailler, John F. Bower
Summary: Under Rh-catalyzed conditions, secondary amines and anilines serve as directing groups, enabling regioselective C-C bond activation of nonactivated cydopropanes. The resulting amino-stabilized rhodacydes undergo carbonylative C-N bond formation to yield challenging seven- and eight-membered lactams, exploiting the rare oxidative addition of C-C bonds of nonactivated cyclopropanes in reaction design.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Jamie A. Cadge, Paul J. Gates, John F. Bower, Christopher A. Russell
Summary: This research reports a newly discovered gold(III) metallafluorene complex that can be used for the synthesis of stable 9-fluorenone products through migratory insertion of CO. This finding expands the potential of using gold chemistry for product synthesis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Changcheng Jing, Benjamin T. Jones, Ross J. Adams, John F. Bower
Summary: Unique examples of aza-Heck-based C(sp3)-H functionalization cascades are described, where alkyl-Pd(II) intermediates generated from the aza-Heck-type cyclization of N-(pentafluorobenzoyloxy)carbamates undergo C(sp(3))-H palladation to form cyclopropanes. The key factors controlling the site selectivity of the cyclopropanation process have been elucidated, enabling selective access to a wide range of ring- or spiro-fused systems.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Sangyun Kim, Annika D. S. Richardson, Atanu Modak, Nicholas J. Race
Summary: We report a dual-catalytic enantioselective allylic alkylation reaction that allows for the synthesis of alpha-amino heteroaryl benzylamine stereocenters with high yield and enantioselectivity.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Olga O. Sokolova, Andrew G. Dalling, John F. Bower
Summary: This Account focuses on C-C bond activation based methodologies using minimally activated cyclopropanes, which allow for the atom economical assembly of complex scaffolds.
Article
Chemistry, Multidisciplinary
Samuel C. Scott, Jamie A. Cadge, Grace K. Boden, John F. Bower, Christopher A. Russell
Summary: We presented a Au-I complex of a hemi-labile (C boolean AND N) N-heterocyclic carbene ligand which can catalyze the oxidative addition of aryl iodides. Extensive computational and experimental investigations were performed to confirm and rationalize the oxidative addition process. The application of this initiation mode led to the first examples of exogenous oxidant-free Au-I/Au-III catalyzed 1,2-oxyarylations of ethylene and propylene. These challenging yet powerful processes establish these commodity chemicals as nucleophilic-electrophilic building blocks in catalytic reaction design.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yuxiang Zhu, Matthew J. S. Smith, Wenbin Tu, John F. Bower
Summary: TFA promotes deprotection of O-Ts activated N-Boc hydroxylamines, leading to aminofunctionalization-based polycyclizations of tethered alkenes. The method enables a range of intramolecular alkene anti-1,2-difunctionalizations, including diamination, amino-oxygenation, and amino-arylation. It offers a predictable platform for accessing diverse C(sp(3))-rich polyheterocycles relevant to medicinal chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Matthew J. S. Smith, Wenbin Tu, Craig M. Robertson, John F. Bower
Summary: This article introduces an aminative cyclization reaction under acidic conditions, which is triggered by the deprotection of BocNR(OSO2R) reagents and carried out on alkenes equipped with pendant nucleophiles. The method offers flexibility in terms of choosing nucleophiles, alkenes, and cyclization modes, and enables the construction of consecutive stereocenters under operationally simple conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Phillippa Cooper, Andrew G. Dalling, Elliot H. E. Farrar, Timothy P. Aldhous, Simon Grelaud, Eleanor Lester, Lyman J. Feron, Paul D. Kemmitt, Matthew N. Grayson, John F. Bower
Summary: The Ir-catalyzed alkene hydroarylation allows for the efficient synthesis of quaternary benzylic centers, and the structural features of the ligand play a crucial role in the reaction efficiency.
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.
