Review
Chemistry, Multidisciplinary
K. R. Holman, A. M. Stanko, S. E. Reisman
Summary: Palladium-catalyzed cascade cyclizations are powerful synthetic tools for assembling polycyclic scaffolds rapidly with high selectivity. By combining multiple ring-forming steps into a single cascade sequence, complex structures can be accessed efficiently, and this strategy has been successfully applied to the synthesis of various natural products.
CHEMICAL SOCIETY REVIEWS
(2021)
Article
Chemistry, Organic
Chaoyi Wu, Jin Lin, Xu Tian
Summary: An efficient Mizoroki-Heck/amination cascade reaction of o-dihaloarenes with cyclic imines was achieved using nickel and a sterically bulky N-heterocyclic carbene ligand. This method provides a straightforward synthesis of a variety of indole[2,1-a]isoquinolines from readily available starting materials. The cascade approach is applicable for the synthesis of the natural product cryptowoline.
Article
Chemistry, Organic
Yu-Jiao Wang, Tong-Tong Wang, Cai-Cai Liang, Zi-Hao Li, Li-Ming Zhao
Summary: An efficient synthesis method for indolo[2,1-a]-benzazepinones has been developed through rhodium-catalyzed cascade reactions of 2-arylindoles with allyl alcohols. This work expands the scope of products available through C-H activation/intramolecular annulation reactions of 2-arylindoles in organic synthesis.
Article
Chemistry, Organic
Luo-Rong Yuan, Shun-Jun Ji, Xiao-Ping Xu
Summary: In this study, a cobalt-catalyzed coupling-cyclization cascade reaction was investigated, which allowed for the synthesis of various spiroindoline compounds by modifying substituents at the N1- and C2-positions in the indole skeleton. Interestingly, the spiroindoline products could undergo despirocyclization in the presence of amines, enabling efficient construction of enamine compounds.
Article
Chemistry, Multidisciplinary
Anil Balajirao Dapkekar, Gedu Satyanarayana
Summary: We report a metal, oxidant, and base-free electrochemical approach for the synthesis of 3-selenylindoles through an oxidative cyclization reaction. This environmentally friendly method demonstrated a wide substrate scope under mild reaction conditions in an electrochemical undivided cell setup.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Miao Hu, Ziying Wu, Biao Yao, Jianxiao Li, Wanqing Wu, Huanfeng Jiang
Summary: A Pd-catalyzed cascade cyclization was developed for the synthesis of (E)-alpha,beta-unsaturated carbonyl compounds, with the sequential formation of C-C bonds. This method offers high efficiency, good functional group tolerance, and moderate to excellent yields, and generally displays high stereoselectivity.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yu-Ping He, Jian Cao, Hua Wu, Qian Wang, Jieping Zhu
Summary: Domino processes initiated by intramolecular nucleopalladation of alkynes have been developed as powerful synthetic tools for functionalized heterocycle synthesis, but catalytic enantioselective versions of these reactions are scarce. By reacting 2-alkynylanilines with prochiral cyclopentenes in the presence of specific catalysts and oxidants, structurally diverse indole-cyclopentene conjugates bearing two stereocenters can be obtained in a highly diastereo- and enantio-selective manner, with one product convertible to heavily functionalized tetracyclic indolinone derivative.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Editorial Material
Nanoscience & Nanotechnology
Miriam S. Vitiello, Luigi Consolino, Massimo Inguscio, Paolo De Natale
Summary: QCL is the most powerful chip-scale source of optical frequency combs, allowing mode proliferation with large quantum efficiencies. THz QCL FCs have promising applications in various fields due to their high quantum efficiency and ease of integration.
Article
Chemistry, Organic
Xingrong Liao, Fulin Zhou, Zhengyang Bin, Yudong Yang, Jingsong You
Summary: The study presents a palladium-catalyzed method for the intermolecular dearomative annulation of aryl halides with alkynes to obtain structurally unique polycyclic aromatic compounds, which could serve as potential host materials for OLEDs. Optoelectronic studies showed a produced PhOLED device with a high maximum external quantum efficiency of 23.0%.
Article
Chemistry, Multidisciplinary
Nandkishor Prakash Khot, Nitish Kumar Deo, Manmohan Kapur
Summary: In this study, a novel vinylogous reactivity of vinyl diazo esters in the C-H bond allylation of benzamides has been developed by combining cobalt and photoredox catalysis. The key factor for the success of this reaction is the close interaction between the high valent cobalt catalyst and the photocatalyst. The reaction utilizes oxygen as the sole oxidant and only generates benign nitrogen as a by-product. It demonstrates a broad substrate scope for both vinyl diazo esters and benzamides.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Wei-Dong Lu, Yu Zheng, Zhi-Peng Zhang, Hong-Bin Chen, Kai Chen, Hao-Yue Xiang, Hua Yang
Summary: In this study, a visible-light-induced palladium-catalyzed desaturation/sulfonation cascade is reported, providing a concise method for the synthesis of highly valuable 4-sulfonyltetrahydropyridine scaffolds from inexpensive and readily available piperidine derivatives with sodium sulfinates. The success of this transformation relies on the well-designed sequence of palladium-mediated 1,5-hydrogen atom transfer/β-hydride elimination/allylic sulfonation process, highlighting the potential of orchestrating synthetic events through rational utilization of varied catalytic modes.
Article
Chemistry, Multidisciplinary
Jiahang Lv, Binlin Zhao, Ying Han, Yu Yuan, Zhuangzhi Shi
Summary: The study presents a novel metal-free catalytic method for successful carbene transfer reactions of alkynes with diazo compounds to form C-C bonds, leading to the preparation of C3-substituted indoles. This strategy shows broad functional group compatibility and can also be extended to construct substituted benzofurans.
CHINESE CHEMICAL LETTERS
(2021)
Article
Biochemistry & Molecular Biology
Yurii V. Kharitonov, Elvira E. Shults
Summary: Isospongian diterpenes are natural compounds derived from marine organisms that can be synthesized with various substituents on their tetracyclic skeleton, providing new molecules for biological research.
Article
Chemistry, Multidisciplinary
Peter Bellotti, Maximilian Koy, Christian Gutheil, Steffen Heuvel, Frank Glorius
Summary: A highly modular radical cascade strategy based on radical cyclisation/allylic substitution sequence has been described, achieving efficient synthesis between alkyl/aryl bromides, 1,3-dienes, and various nucleophiles. Palladium phosphine complexes play a crucial role in this reaction, enabling 1,4-selectivity and stereocontrol to deliver carbocyclic and heterocyclic structures with important functional groups. Additionally, a flow chemistry approach was applied for the first time in palladium-photocatalysed endeavors involving radicals.
Article
Chemistry, Organic
Namrata Prusty, Shyam Kumar Banjare, Smruti Ranjan Mohanty, Tanmayee Nanda, Komal Yadav, Ponneri C. Ravikumar
Summary: A nickel-catalyzed synthesis method allows for selective functionalization of indole and establishment of heteropolycyclic aromatic motifs through C-H functionalization, showing good adaptability to both aromatic internal alkynes and aliphatic alkynes. Notably, catalytic enhancement with sodium iodide as an additive was observed during optimization, and the photophysical properties of highly conjugated molecules were also studied.
Article
Chemistry, Organic
Carlos Palo-Nieto, Abhijit Sau, Robin Jeanneret, Pierre-Adrien Payard, Aude Salame, Maristela Braga Martins-Teixeira, Ivone Carvalho, Laurence Grimaud, M. Carmen Galan
Article
Chemistry, Applied
Sudipta Ponra, Aude Nyadanu, Na Pan, Elodie Martinand-Lurin, Alexandra Savy, Maxime R. Vitale, Laurent El Kaim, Laurence Grimaud
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2020)
Article
Chemistry, Organic
Mansour Dole Kerima, Pakoupati Boyode, Julian Garrec, Laurent El Kaim
Article
Chemistry, Inorganic & Nuclear
Pierre-Adrien Payard, Luca Alessandro Perego, Laurence Grimaud, Ilaria Ciofini
Article
Chemistry, Multidisciplinary
Cristina Cheibas, Nicolas Fincias, Nicolas Casaretto, Julian Garrec, Laurent El Kaim
Summary: The Passerini-Smiles reactions of alpha-ketophosphonates with nitrophenols have been studied, revealing complex cascades involving multiple Smiles transfers and phospha-Brook rearrangement. The use of 4-nitrophenols leads to a rare 1,3-Truce-Smiles rearrangement, while 2-nitro derivatives show a different reactivity pattern possibly due to a nitro to nitroso conversion followed by a sigma-pi metathesis. DFT calculations support the proposed mechanisms for both families of adducts, and the potential of this work is further demonstrated by alternative starting materials and the discovery of new aza-Nazarov access.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Shan Dai, Kieu Phung Ngoc, Laurence Grimaud, Sanjun Zhang, Antoine Tissot, Christian Serre
Summary: Metal nanoparticles encapsulated in a MOF shell show remarkable catalytic properties, but commonly used capping agents decrease their reactivity. In this study, we developed a new method to prepare PVP-capped Au NPs@MOF-808 core-shell composites, and demonstrated for the first time that the capping PVP can be easily removed while maintaining the integrity of the MOF shell. The reactivity of the Au NPs@MOF-808 composites for selective oxidation reactions was significantly enhanced.
JOURNAL OF MATERIALS CHEMISTRY A
(2022)
Article
Chemistry, Multidisciplinary
Agnideep Das, Jules Schleinitz, Lydia Karmazin, Bruno Vincent, Nolwenn Le Breton, Guillaume Rogez, Aurelie Guenet, Sylvie Choua, Laurence Grimaud, Marine Desage-El Murr
Summary: Mechanisms combining organic radicals and metallic intermediates have great potential in homogeneous catalysis. This study reports the use of a bioinspired polymetallic nickel complex that can perform fast hydrosilylation of alkenes through a dual radical- and metal-based mechanism. The complex operates at low catalyst loading and generates silyl radicals and a nickel-hydride intermediate through a hydrogen atom transfer step. Evidence suggests the involvement of the nickel-hydride species in chain walking, enabling terminal hydrosilylation of internal alkenes. This single catalyst promotes a hybrid pathway by combining ligand and metal participation in both inner- and outer-sphere processes.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Jules Schleinitz, Maxime Langevin, Yanis Smail, Benjamin Wehnert, Laurence Grimaud, Rodolphe Vuilleumier
Summary: This study focuses on the application of machine learning in predicting synthetic yields and builds a dataset based on organic reaction publications. The study finds that including optimization data improves prediction accuracy and emphasizes the impact of publication constraints on the exploration of chemical space by the synthetic community.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Cristina Cheibas, Emilie Vieu, Nicolas Casaretto, Maxime Vitale, Laurence Grimaud, Laurent El Kaim
Summary: Ugi adducts involving malonic acid monoesters and di-alkoxy-substituted aromatic aldehydes can undergo an oxidative dearomatization when treated with Mn(OAc)(3), resulting in the formation of fused cyclopropanes similar to the Buchner reaction of diazo compounds.
Article
Chemistry, Inorganic & Nuclear
Cheriehan Hessin, Jules Schleinitz, Nolwenn Le Breton, Sylvie Choua, Laurence Grimaud, Vincent Fourmond, Marine Desage-El Murr, Christophe Leger
Summary: Potential inversion refers to the phenomenon where the second electron transfer is easier than the first, and it is significant for understanding enzyme catalysis and developing efficient catalysts. Currently, there is a lack of analytical predictions to interpret voltammetric peak potentials when potential inversion occurs, and cyclic voltammograms are often analyzed without considering overfitting or estimating error. In this study, a theory for voltammetry of two-electron redox species in the irreversible limit is formulated and applied to analyze the voltammetry of a nickel complex with redox-active ligands, highlighting the intrinsic underdetermination of the model. Characterizing the thermodynamics of two-electron electron-transfer reactions is crucial for catalyst design.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Jordan Rio, Haosheng Liang, Marie-Eve L. Perrin, Luca A. A. Perego, Laurence Grimaud, Pierre-Adrien Payard
Summary: This perspective presents a summary of selected mechanistic studies of the Pd(0)-to-Pd(II) oxidative addition process involving organic halides and pseudohalides, with a focus on systems relevant to catalytic reactions. The results are classified and described according to the nature of supporting ligands, highlighting general trends and the most relevant examples. The survey includes the formation of active species from precatalysts and the influence of different species present under catalytic conditions on the oxidative addition process, providing guidelines for improving the understanding and efficiency of catalytic reactions.
Review
Chemistry, Physical
Laurence Grimaud, Sami Lakhdar, Maxime R. Vitale
Summary: Although the concept of combining electrosynthesis with photochemistry has been around for many years, its practical application in organic synthesis has only recently emerged. This article highlights the power of this technology and how it can be used to overcome challenging oxidative or reductive processes. It presents recent chemical transformations that are otherwise inaccessible and discusses the important challenges and opportunities in this vibrant research field.
CURRENT OPINION IN ELECTROCHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Georgina Kirby, Laurence Grimaud, Maxime R. Vitale, Guillaume Prestat, Farouk Berhal
Summary: The iron-catalyzed intermolecular aziridination of alkenes with hydroxylamine derivatives was successfully achieved by using simple methods to synthesize a variety of aziridines. The sustainable reaction conditions allowed for high yields of products to be obtained. Preliminary mechanistic studies suggest the operation of both concerted and stepwise pathways in this transformation.
Article
Chemistry, Multidisciplinary
Na Pan, Maegan Xinen Lee, Louis Bunel, Laurence Grimaud, Maxime R. Vitale
Summary: Oxidative isocyanide-based multicomponent reactions are useful tools for rapid construction of molecular diversity, but are currently underdeveloped and limited to 3-component processes. By using a mild and green oxidation process, we can overcome selectivity challenges and involve more reaction partners.
ACS ORGANIC & INORGANIC AU
(2021)
Article
Chemistry, Multidisciplinary
Na Pan, Maegan Xinen Lee, Louis Bunel, Laurence Grimaud, Maxime R. . Vitale
Summary: Oxidative isocyanide-based multicomponent reactions are useful tools for rapidly building molecular diversity from readily available and stable substrates. However, the chemo-selectivity of the oxidation event becomes more intricate as the number of reactive components increases in such reactions.
ACS ORGANIC & INORGANIC AU
(2021)
