Article
Chemistry, Multidisciplinary
Ming-Yao Huang, Shou-Fei Zhu
Summary: In comparison to common carbene insertion reactions, the overlooked uncommon carbene insertion reactions have been gaining more attention recently for their synthetic potential. The perspective reviews the history and latest advances of uncommon carbene insertion reactions, discusses their potential applications and challenges, and provides an outlook for this promising field.
Article
Chemistry, Multidisciplinary
Xun-Shen Liu, Zhiqiong Tang, Zhi-Yao Si, Zhikun Zhang, Lei Zhao, Lu Liu
Summary: Asymmetric para-C(sp(2))-H bond functionalization of alkyl benzene derivatives was successfully achieved via cooperative catalysis of gold and chiral phosphoric acid (CPA). This method offers mild conditions, high efficiency, broad substrate scope, and extensive applications of the chiral products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Qing Sun, Yuzhu Peng, Yujing Wang, Xiaoguang Bao
Summary: Here, a photoredox-catalyzed insertion reaction of sulfoxonium ylides with carboxylic acids is reported, providing a practical method for the preparation of a-acyloxy ketones with a wide range of carboxylic acids under mild and simple conditions. Experimental and computational studies suggest a stepwise proton-assisted electron transfer mechanism for this reaction.
Article
Chemistry, Organic
Yong Wu, Yongquan Ning, Xinyue Han, Peiqiu Liao, Ying Xia, Paramasivam Sivaguru, Xihe Bi
Summary: The silver-catalyzed formal insertion of a vinylcarbene into unstrained C(CO)-C bonds of 1,3-diketones using vinyl-N-triftosylhydrazones as precursors allows for the rapid synthesis of 2-vinyl-substituted 1,4-diketones with good functional group tolerance and substrate scope. Preliminary theoretical calculations suggest that the reaction proceeds through a stepwise enol cyclopropanation/retro-aldol pathway.
Article
Chemistry, Multidisciplinary
Kristine Klimovica, Julius X. Heidlas, Irvin Romero, Thanh V. Le, Olafs Daugulis
Summary: This article reports sandwich diimine-copper(I) catalysts for C(sp(3))-H bond functionalization, demonstrating rare examples of base-metal catalyzed, intermolecular C(sp(3))-H functionalizations using unactivated diazo compounds. The electrophilicity and unique steric environment of the sandwich-copper catalysts are likely reasons for their catalytic efficiency.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Neha Jha, Nandkishor Prakash Khot, Manmohan Kapur
Summary: The past decade has seen significant advancements in transition-metal-catalyzed C-H bond activation and carbene migratory insertion reactions, facilitating the construction of diverse arene/heteroarene scaffolds. Various transition-metal catalysts are utilized for easy access to substituted heterocycles, with key mechanistic pathways involving C-H activation, diazo insertion, and subsequent coupling reactions.
Article
Chemistry, Multidisciplinary
Yangyang Yang, Jet Tsien, Ayala Ben David, Jonathan M. E. Hughes, Rohan R. Merchant, Tian Qin
Summary: This research introduces a new transition-metal-free mediated transformation for the construction of C(sp(3))-rich and sterically hindered alkyl boron reagents. The method shows broad generality and functional group tolerance, making it suitable for the synthesis and functionalization of medicinal chemistry scaffolds. The strategic significance of using alkyl boronic acids as linchpins is demonstrated through downstream functionalizations of the alkyl boron compounds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Haruki Mizoguchi, Ryuji Yoshida, Haruka Ikeda, Akira Sakakura
Summary: An intramolecular C-H silylmethylation of benzylic alcohol derivatives was achieved using a visible-light-photoexcited palladium complex as the catalyst. Blue LED irradiation activated a C-I bond, and subsequent intramolecular radical arylation led to the formation of siloxacycle products. Selective protonation or oxidation of the C-Si bond of the cyclized materials afforded ortho-methylated and ortho-hydroxymethylated derivatives of the benzylic alcohol derivatives.
Article
Chemistry, Organic
Fei Wang, Junyi Yi, Yoshihiro Nishimoto, Makoto Yasuda
Summary: The homologation of alkyl acetates, alkyl ethers, acetals, and ketals was achieved through the formal insertion of diazo esters into carbon-carbon sigma-bonds. The use of the Lewis acids InI3 with Me-3SiBr catalyzed the homologation of alkyl acetates and alkyl ethers, while InBr3 catalyzed that of acetals and ketals. The appropriate Lewis acidity of the indium-based Lewis acids played a key role in both the abstraction and release of leaving groups, leading to the formation of homologated products.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Organic
Chuan-Ming Hong, Si-Qi Xiong, Xue Zhang, Kai-Xian Ma, Qing-Hua Li, Tang-Lin Liu
Summary: This paper discloses a silver-catalyzed 1,3-aza-benzyl migration of allyl alcohols by utilizing chelation-assisted selective cleavage of an unstrained C(sp3)-C(sp3) bond. This approach provides an available, efficient, high atom-economic, and environmentally benign procedure, leading to alkylation products with broad substrate scopes and excellent yields. The migration proceeds via a one-pot, two-step process involving a free-state alkyl metal species.
Article
Chemistry, Multidisciplinary
Kaito Kuroki, Tatsuyoshi Ito, Jun Takaya
Summary: By utilizing a photo-promoted skeletal rearrangement reaction, borabicyclo[3.2.0]heptadiene derivatives were successfully synthesized via boron-insertion into aromatic C-C bonds. The reverse reaction of dearomatized products was observed to occur in the dark at room temperature, achieving a photochemical and thermal interconversion between triarylboranes and boron-doped bicyclic systems.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Mingshuai Zhang, Longkun Chen, Zhuoyuan Liu, Jiuzhong Huang, Fuchao Yu
Summary: Here, a straightforward method for obtaining 3a,7a-dihydroxy hexahydro-4H-indol-4-ones through Ru(III)-catalyzed alkenyl C(sp(2))-H bond functionalization/[3 + 2] annulation of enaminones with iodonium ylides is described. This protocol offers chemoselectivity, broad substrate scope, moderate to excellent yields, gram-scale synthesis, and mild reaction conditions. The resulting 3a,7a-dihydroxy hexahydro-4H-indol-4-one scaffolds can be easily further modified to 1H-pyrrol-3-ol carboxylate derivatives, showing potential applications in organic synthesis and medicinal chemistry.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Mingshuai Zhang, Longkun Chen, Zhuoyuan Liu, Jiuzhong Huang, Fuchao Yu
Summary: In this study, a straightforward and efficient method for the synthesis of 3a,7a-dihydroxy hexahydro-4H-indol-4-ones via Ru(iii)-catalyzed alkenyl C(sp(2))-H bond functionalization/[3 + 2] annulation of enaminones with iodonium ylides is described. The method exhibits chemoselectivity, broad substrate scope, moderate to excellent yields, gram-scale synthesis, and mild reaction conditions.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Neha Jha, Roushan Prakash Singh, Paridhi Saxena, Manmohan Kapur
Summary: An Ir(III)-catalyzed C(3)-H alkylation of N-acetyl-1,2-dihydroisoquinolines with diverse acceptor-acceptor diazo compounds has been achieved under a single catalytic system via metal carbene migratory insertion. Further synthetic transformations of the alkylated products lead to the formation of several synthetically viable isoquinoline derivatives with immense potentials.
Article
Chemistry, Organic
Lei Chen, Rui-jun Peng, Xue-jing Zhang, Ming Yan, Albert S. C. Chan
Summary: The Rh(III)-catalyzed migratory insertion of bis(phenylsulfonyl)carbene into aromatic C-H bonds has been developed to synthesize various bis(phenylsulfonyl)methyl derivatives under mild conditions with good yields. The methylated products can be readily obtained after reductive desulfonylation, and further transformations to trideuteriomethyl, aldehyde, and other functional groups have been demonstrated.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Chaosheng Luo, Juan V. Alegre-Requena, Stephen J. Sujansky, Spencer P. Pajk, Liliana C. Gallegos, Robert S. Paton, Jeffrey S. Bandar
Summary: This study investigates the mechanism of nucleophilic addition of alcohols to simple alkenes, revealing the influence of alcohol stoichiometry on reaction rate and proposing a new solution. The improved method does not require excess alcohol, expands the substrate scope, and utilizes more practical catalyst systems.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Meire Y. Kawamura, Juan Alegre-Requena, Thais M. Barbosa, Claudio F. Tormena, Robert S. Paton, Marco A. B. Ferreira
Summary: [3+2] cycloadditions of nitroolefins are a selective and catalyst-free alternative for synthesizing 1,2,3-triazoles. Mechanistic studies reveal that the rate-limiting step is the cycloaddition, which shows high kinetic selectivity for the formation of 1,5-triazoles.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Thermodynamics
Junqing Zhu, Juan V. Alegre-Requena, Patrick Cherry, Dominic Curtis, Mohammed A. Jabed, Seonah Kim, Charles S. McEnally, Lisa D. Pfefferle, Josanne-Dee Woodroffe
Summary: This study measured the sooting tendencies of terpenes and their derivatives and found that the hydrogenated compounds have lower sooting tendencies, offering benefits in reducing soot.
PROCEEDINGS OF THE COMBUSTION INSTITUTE
(2023)
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, Applied
Sandra Ardevines, Devan Horn, Juan Alegre-Requena, Marta Gonzalez-Jimenez, M. Concepcion Gimeno, Eugenia Marques-Lopez, Raquel P. Herrera
Summary: An enantioselective C-P bond formation has been developed by activating C(sp(3))-H in an oxidation step, followed by an organocatalytic hydrophosphonylation protocol. The Pudovik reaction achieved asymmetric organocatalysis using a one-pot strategy with different alcohols and phosphite, MnO2 as the oxidant, and a chiral squaramide as the organocatalyst. The reaction scope produced enantiomerically enriched a-hydroxy phosphonates with yields ranging from 40% to >95% and enantioselectivities from 64% to >99%. Furthermore, this methodology has demonstrated the formation of a tetrasubstituted carbon stereocenter in situ, using diphenyl phosphite, to generate an acetophenone derivative. Therefore, this approach represents an asymmetric strategy for constructing chiral C-P bonds, which is significant for the pharmaceutical industry.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Ranjana Bisht, Mihai V. Popescu, Zhen He, Ameer M. Ibrahim, Giacomo E. M. Crisenza, Robert S. Paton, David J. Procter
Summary: Activated benzothiophenes undergo C-H/C-H-type coupling with phenols to give C4 arylation products without a directing group or a metal catalyst. Quantum chemical calculations propose a stepwise mechanism involving aryloxysulfur species cleavage and addition of phenoxonium cation to C4 position. The metal-free arylation process demonstrates varied selective manipulation of benzothiophene products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Biochemistry & Molecular Biology
Sonia Sierra, David Dalmau, Juan V. Alegre-Requena, Alexandra Pop, Cristian Silvestru, Maria Luisa Marin, Francisco Bosca, Esteban P. Urriolabeitia
Summary: Under blue light irradiation, the 2-aryl-4-(E-3'-aryl-allylidene)-5(4H)-oxazolones 1 underwent [2+2]-photocycloaddition to form the unstable cyclobutane-bis(oxazolones) 2. Treatment with NaOMe/MeOH led to the ring-opening reaction of 2 and the formation of stable styryl-cyclobutane bis(amino acids) 3.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Multidisciplinary
Matthew A. Horwitz, Alexander B. Durr, Konstantinos Afratis, Zijun Chen, Julia Soika, Kirsten E. Christensen, Makoto Fushimi, Robert S. Paton, Veronique Gouverneur
Summary: The controlled programming of regiochemical outcomes in nucleophilic fluorination reactions with alkali metal fluoride is achieved through two synergistic approaches exploiting hydrogen bonding catalysis. The charge density of fluoride is modulated with a hydrogen-bond donor urea catalyst to influence the kinetic regioselectivity in the fluorination of dissymmetric aziridinium salts. Additionally, a urea-catalyzed formal dyotropic rearrangement is reported, allowing access to enantioenriched fluoroamine regioisomers and providing new opportunities in regiodivergent asymmetric (bis)urea-based organocatalysis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Owen Smith, Mihai V. Popescu, Madeleine J. Hindson, Robert S. Paton, Jonathan W. Burton, Martin D. Smith
Summary: This paper reports the design, synthesis and characterization of a helically chiral triaryloxonium ion that functions as a determinant of configuration. It is the only example of a chiral non-racemic and configurationally stable molecule in which the oxygen atom is the sole stereogenic centre.
Article
Chemistry, Physical
Peng Zhang, Chang-Qiu Guo, Wang Yao, Chuan-Jun Lu, Yingzi Li, Robert S. S. Paton, Ren-Rong Liu
Summary: A palladium-catalyzed amination method was developed to construct structurally diverse N-C atropisomers, and the reaction mechanism was explained using density functional theory calculations. This method has a broad substrate scope, high stereoselectivity, a simple catalytic system, good functional group tolerance, and dynamic kinetic resolution.
Article
Chemistry, Multidisciplinary
Juan V. Alegre-Requena, Sowndarya S. Shree, Raul Perez-Soto, Turki M. Alturaifi, Robert S. Paton
Summary: AQME is a free and open-source Python package for automated workflows in cheminformatics and quantum chemistry. It integrates tasks across multiple computational chemistry packages and data formats, preserving computational protocols, data, and metadata for access and reuse. AQME has a modular structure and can be used by researchers familiar with Python.
WILEY INTERDISCIPLINARY REVIEWS-COMPUTATIONAL MOLECULAR SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Jeong-Yu Son, Santeri Aikonen, Nathan Morgan, Alexander S. Harmata, Jesse J. Sabatini, Rosario C. Sausa, Edward F. C. Byrd, Daniel H. Ess, Robert S. Paton, Corey R. J. Stephenson
Summary: Cuneane, a strained hydrocarbon, can be accessed via metal-catalyzed isomerization of cubane. It has a polyhedral structure with six faces of different shapes. The rigidity and unique properties make it a potential scaffold for the synthesis of small molecules and materials. However, previous synthetic efforts have been limited to monosubstituted or redundantly substituted cuneanes, and more complex substitution patterns are needed for the study of this ring system in various applications.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Multidisciplinary Sciences
Calum Patel, Emy Andre-Joyaux, Jamie A. Leitch, Xabier Martinez de Irujo-Labalde, Francesco Ibba, Job Struijs, Mathias A. Ellwanger, Robert Paton, Duncan L. Browne, Gabriele Pupo, Simon Aldridge, Michael A. Hayward, Veronique Gouverneur
Summary: This article introduces a method of reacting acid-grade fluorspar with dipotassium hydrogen phosphate under mechanochemical conditions, resulting in a solid product suitable for forming sulfur-fluorine and carbon-fluorine bonds.
Article
Chemistry, Multidisciplinary
S. V. Shree Sowndarya, Yeonjoon Kim, Seonah Kim, Peter C. St. John, Robert S. Paton
Summary: This study advances the accuracy and applicability of machine learning in predicting bond dissociation energy by expanding and updating the model. The new model includes more elements and bond types, and successfully improves predictive accuracy by introducing more training data, which is of great significance for the application of molecules in medicine and the environment.
