Article
Chemistry, Physical
Claire Empel, Sripati Jana, Adithyaraj Koodan, Rene M. Koenigs
Summary: In this study, a photocatalytic orthoalkylation reaction was reported, which achieved the reaction between 2-phenyl pyridines and N-protected maleimides using a catalyst and an additive at room temperature. Experimental and theoretical studies revealed a reaction mechanism that involved both dark and light reactions, with the photochemical excitation facilitating the ligand exchange and protodemetalation reaction.
Article
Chemistry, Physical
Zhiqian Yu, Qianhui Liu, Yudong Yang, Jingsong You
Summary: This study demonstrates that phenolic compounds can serve as effective ligands to control the regioselectivity of ortho-C-H arylation reactions, enabling the synthesis of various biaryl phosphines in a streamlined and practical manner. The phosphine ligand library shows great potential in catalytic coupling reactions and exhibits unique chemoselectivity when compared with commercially available classic phosphine ligands.
Article
Chemistry, Physical
Lingheng Kong, Xi Han, Haohua Chen, Huaming Sun, Yu Lan, Xingwei Li
Summary: The regioselective coupling of NH indoles with diazo compounds using dimeric Rh(II) complexes as catalysts demonstrates selectivity towards C(6) or C(7) positions depending on the structure of the indoles. Mechanistic studies reveal that hydrogen-bonding directing effect plays a crucial role in determining the regioselectivity, with C-C bond formation proceeding through Friedel-Crafts-type attack. This work highlights the challenges and opportunities in controlling regioselectivity in reactions involving arene C-H bonds.
Article
Multidisciplinary Sciences
Shao-Bai Yan, Rui Wang, Zha-Gen Li, An-Na Li, Chuanyong Wang, Wei-Liang Duan
Summary: This paper reports a Cu-catalyzed asymmetric C(sp(2))-H arylation using diaryliodonium salts, which enables the synthesis of a range of chiral phosphonic diamides and chiral phosphine oxide indoles with high selectivity under mild conditions.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Yanhui Guo, Li Wei, Zhonglin Wen, Huanfeng Jiang, Chaorong Qi
Summary: An efficient photoredox-catalyzed three-component coupling reaction of aryl sulfonium salts, carbon dioxide and amines has been developed for the first time. This synthesis provides a new strategy for the preparation of valuable O-aryl carbamates from readily available arenes. The method demonstrates mild conditions, a broad substrate scope and good functional group tolerance, making it useful for late-stage modification of bioactive molecules and pharmaceuticals.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Guanghua Kuang, Dandan Liu, Xuerong Chen, Guangyuan Liu, Yang Fu, Yiyuan Peng, Hua Li, Yirong Zhou
Summary: A unified method for direct C4-H halogenation of indoles has been successfully achieved with the assistance of anthranilic acids as suitable transient directing groups. Exclusive site selectivity and good functional group tolerance were obtained using inexpensive N-halosuccinimides as halogen sources under mild conditions. The rich functional groups in the product allow for facile construction of a diversity of nitrogen-containing heterocycles via one-step late-stage derivations.
Article
Chemistry, Physical
Ouidad Lahtigui, Dan Forster, Coralie Duchemin, Nicolai Cramer
Summary: In this study, a flexible two-step protocol for the efficient and selective synthesis of rigid saturated nitrogen-containing scaffolds was disclosed. The method involves alkenyl C-H functionalization and cyclization reactions mediated by C*Rh-III and Cp*Ir-III catalysts, respectively, leading to the synthesis of diverse substituted 3-azabicyclo[3.1.0]hexanes.
Article
Chemistry, Multidisciplinary
Bin Zhao, Zichen Pan, Jiayu Pan, Hongping Deng, Xiaoli Bu, Mengtao Ma, Fei Xue
Summary: We report a regiodivergent defluorinative carboxylation of gem-difluorocyclopropanes achieved by subtly modulating the electrochemical conditions. This method allows for the selective synthesis of branched and linear monofluoroalkene carboxylic acids in moderate to high yields and with exclusive regioselectivities. The protocol is green, using atmospheric CO2 as the C1 source and not requiring transition metals, and can be scaled up and applied to late-stage functionalization of complex compounds.
Article
Chemistry, Physical
Shrikant M. Khake, Naoto Chatani
Summary: The Rh(III)-catalyzed C-H oxidative alkylation of aniline derivatives with readily available secondary allyl alcohols is described. The reaction exhibited tolerance towards various functional groups. Different oxidants are required depending on the structure of the allyl alcohol. Mechanistic experiments revealed insights into the catalyst regeneration step.
Article
Chemistry, Organic
Takeshi Nanjo, Hikari Sada, Taisei Nagaya, Yuri Maruo, Yoshiji Takemoto
Summary: In this study, a cationic rhodium catalyst and methyl trifluoroborate salt were used to achieve the stereoselective formation of beta,beta-disubstituted dehydroamino acids (ΔAAs) in peptides. This method allowed the direct installation of an alkyl group on a beta-monosubstituted ΔAA in the peptide chain, leading to the successful synthesis of both isomers of dehydroisoleucine, which is an important yet usually inaccessible ΔAA.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Takanobu Saito, Joaquim Caner, Naoyuki Toriumi, Nobuharu Iwasawa
Summary: A novel method for the meta-selective C-H carboxylation of 1,1-diarylethylene derivatives using a rhodium catalyst and a stoichiometric reductant has been achieved. The introduction of a carboxyl group to the aryl ring at the meta-position was enabled with high selectivity. Both experimental and computational mechanistic studies indicate that a specific rhodium migration process plays a key role in this unusual aryl-to-aryl 1,2-rhodium shift.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Yufeng Du, Linyu Huang, Neng Wang, Xiaohuan Li, Xian-Li Zhou, Lan Zhang, Shuai Huang, Patrick J. Walsh, Feng Gao
Summary: A Rh-2(OAc)(4)/IMes . HCl system is reported in this study, which enables the chemoselective installation of aryl groups at the 2-position of furo[2,3-b]pyridine with yields ranging from 53% to 94%. The modified furoquinoline alkaloid dictamnine shows improved cardiac effects compared to the natural compound, possibly through interactions with epinephrine alpha receptors, M-receptors, and calcium channel receptors.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Multidisciplinary Sciences
Shi Cao, Wei Hong, Ziqi Ye, Lei Gong
Summary: The study demonstrates the use of a dual asymmetric photocatalyst leading to the development of asymmetric sulfonylation involving direct functionalization of cycloalkanes, alkanes, toluene derivatives or ethers.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Zeyu Shao, Junqi Zhou, Ziyu Wang, Biao Liu, Liang-Hua Zou, Cheng Wang, Jian Wen
Summary: A metal-free allylic C(sp(3))-H alkylation method based on [2,3]-sigmatropic rearrangement strategies has been developed, allowing the allylic C(sp(3))-H alkylation of a wide range of alpha-alkylstyryl sulfonium salts. This protocol enables facile access to allylated carbon quaternary centers in moderate to good yields. The one-pot procedure, product derivatization, and late-stage functionalization demonstrate the practicality of this protocol in organic synthesis.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Shengjun Ni, Matic Hribersek, Swarna K. Baddigam, Fredric J. L. Ingner, Andreas Orthaber, Paul J. Gates, Lukasz T. Pilarski
Summary: This new mechanochemical method enables highly regioselective C-H methylation of (hetero)arenes, showing excellent functional-group compatibility and shorter reaction times, and can be used for the synthesis of biologically active compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Amal Benzai, Fazia Derridj, Henri Doucet, Jean-Francois Soule
Summary: The study reports a Pd- or Ru-catalyzed arylation reaction that allows for the ortho-arylation of the aryl unit of 2-arylpyrazines with high regioselectivity and applicability to various substituted pyrazine compounds. Experimental results demonstrate that even pyrazines with 2,3-diphenyl substitution can yield the desired arylated product.
Article
Chemistry, Multidisciplinary
Xinzhe Shi, E. Daiann Sosa Carrizo, Marie Cordier, Julien Roger, Nadine Pirio, Jean-Cyrille Hierso, Paul Fleurat-Lessard, Jean-Francois Soule, Henri Doucet
Summary: Selective arylation at the beta-position of pyrazoles under ligand-free palladium catalysis with a simple base, without the need for an oxidant or further additives, is reported. The reaction proceeds smoothly with a variety of N-substituted pyrazoles using aryl bromides as the aryl source and a protic solvent. This beta-C-H bond arylation enables the construction of pi-extended poly(hetero)aromatic structures via further Pd-catalyzed combined alpha-C-H intermolecular and intramolecular C-H bond arylation, offering an atom-economical process.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Xinzhe Shi, Jian Zhang, Thierry Roisnel, Jean-Francois Soule, Henri Doucet
Summary: The reactivity of 2-benzyl-1,2,3-triazole in palladium-catalyzed direct arylation was investigated, leading to the selective synthesis of 2-benzyl-4-aryl-1,2,3-triazoles and subsequent synthesis of 4,5-diarylated 2-benzyl-1,2,3-triazoles. This selective 4,5-diarylation was successfully applied for the synthesis of pi-extended polycyclic heteroaromatic structures phenanthro[9,10-d][1,2,3]triazoles through Pd-catalyzed C4- and C5-intermolecular arylations followed by Pd-catalyzed C-H intramolecular arylation.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Editorial Material
Chemistry, Inorganic & Nuclear
Jean-Francois Soule, Christian Bruneau, Christophe Darcel
Article
Chemistry, Multidisciplinary
Marie Peng, Jinqiang Lin, Wei Lu, Thierry Roisnel, Veronique Guerchais, Henri Doucet, Jean-Francois Soule
Summary: The utility of C-H bond functionalization of metalated ligands for the elaboration of aryl-functionalized difluorinated-1-arylisoquinolinyl Ir(III) complexes has been explored, resulting in the regioselective arylation of C-H bonds flanked by difluoroaryl units. Post-functionalization allows for the introduction of thermally sensitive functional groups, and all obtained complexes emit red phosphorescence with similar lifetimes.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Zhuan Zhang, Natacha Durand, Jean-Francois Soule
Article
Chemistry, Multidisciplinary
Yi-Xuan Cao, Gan Zhu, Yiqun Li, Nolwenn Le Breton, Christophe Gourlaouen, Sylvie Choua, Julien Boixel, Henri-Pierre Jacquot De Rouville, Jean-Francois Soule
Summary: A photoinduced arylation method has been developed for N-substituted acridinium salts, leading to a range of well-decorated acridinium-based catalysts with fine-tuned photophysical and photochemical properties. These catalysts exhibited excellent performance in the photoredox-catalyzed fragmentation of 1,2-diol derivatives, particularly the selective cleavage of C beta O-Ar bond in diol monoarylethers.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Javid Rzayev, Zhuan Zhang, Natacha Durand, Jean-Francois Soule
Summary: We report on an Rh(I)-catalyzed C-H bond alkylation of PhenCarPhos and related phosphine ligands with alkenes. The C-H bond functionalization selectively occurs at the C1 position of the carbazolyl unit due to the presence of a trivalent phosphine directing group. This protocol offers a straightforward method to access a diverse library of C1-alkyl substituted PhenCarPhos, which exhibit superior performance compared to common commercial or unfunctionalized phosphines and their precursors in Pd-catalyzed carbon dioxide-fixation reactions with propargylic amines.
Article
Chemistry, Multidisciplinary
Marie Peng, Chang-Sheng Wang, Pan-Pan Chen, Thierry Roisnel, Henri Doucet, K. N. Houk, Jean-Francois Soule
Summary: We describe a Rh(III)-catalyzed ortho-C-H bond functionalization of nitroarenes with 1,2-diarylalkynes and carboxylic anhydrides. The reaction unexpectedly produces 3,3-disubstituted oxindoles with the formal reduction of the nitro group under redox-neutral conditions. This transformation allows the synthesis of oxindoles with a quaternary carbon stereocenter using nonsymmetrical 1,2-diarylalkynes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Maoyi Dai, Yingying Zhang, Xiaoxiang Zhang, Ruiyi Wang, Wanxing Wei, Zhuan Zhang, Taoyuan Liang
Summary: A metal-free one-pot oxidative cross-dehydrogenation coupling reaction has been developed for the formation of C-N/C-C bonds at the C2,3-positions of indoles with azoles and quinoxalinones. The proposed method has several notable features, including metal-free catalysis, the use of N-H free indoles as substrates, ease of operation, mild reaction conditions, and compatibility with a wide range of substrates.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Marie Peng, Denis Ari, Thierry Roisnel, Henri Doucet, Jean-Francois Soule
Summary: We present a versatile Rh(i)-catalyzed cascade reaction that combines C(sp(2))-H bond functionalization and amidation between N-arylphosphanamines and acrylates. This innovative approach allows for the rapid synthesis of dihydroquinolinone scaffolds, which are commonly found in various pharmaceuticals. The involvement of a Rh-H intermediate and the substrate inhibition through catalyst saturation were revealed through detailed mechanistic investigations.
Article
Chemistry, Organic
Xiaoxiang Zhang, Chenrui Liu, Yingying Zhang, Fang Shen, Wanxing Wei, Zhuan Zhang, Taoyuan Liang
Summary: Catalysis by organo-chalconium catalysts, which can bind and activate substrates through attractive, non-covalent interactions, is an important approach in organic and organometallic chemistry. The study presents a new strategy for direct C2,3-H difunctionalization of indoles with unactivated amines using an organo-chalconium catalyst generated from the reaction of iodine and chalconium reagents. This strategy allows for the assembly of complex molecular architectures and late-stage functionalization of natural products and pharmaceutical compounds, optimizing their bioactivity and pharmacokinetic properties.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Xiaoxiang Zhang, Yingying Zhang, Xiaoting Gu, Zhuan Zhang, Wanxing Wei, Taoyuan Liang
Summary: A copper-mediated 2,3-difunctionalization of indoles to afford 3-halogenated 2,3 '-biindoles is described. The protocol uses readily available feedstocks and a naturally abundant copper catalyst system, which allows the regioselective formation of C-C and C-X (X = Cl & Br) bonds in one single operation. Copper metal salt serves not only as a catalyst but also as a reactant to provide the source of halogen, avoiding the use of environmentally unfriendly reagents and displaying good functional group compatibility.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Qiao Sun, Jean-Francois Soule
Summary: Efficient methods for the synthesis of deuterated molecules, particularly CD3-containing ones, have been continuously desired in pharmaceuticals and mechanistic understanding. The recent focus has shifted towards direct incorporating CD3 motifs into molecules, along with the development of various approaches. This review provides an overview of preparation methods for CD3-labeled molecules, ranging from conventional functional group interconversion techniques to catalytic approaches, and includes detailed discussions on reaction mechanisms.
CHEMICAL SOCIETY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Wided Hagui, Marie Cordier, Julien Boixel, Jean-Francois Soule
Summary: A new method for photoredox-mediated C-H bond alkylation of 6-aryl-2,2'-bipyridines with N-(acyloxy)phthalimides has been reported, showing excellent functional group tolerance, including chiral aliphatic groups. The influence of the incorporated C6'-alkyl group on the photophysical properties of the corresponding (N^C^N) cyclometalated Pt(u) complexes, including chiroptical properties, has been described.
CHEMICAL COMMUNICATIONS
(2021)
