Article
Chemistry, Multidisciplinary
Nils L. Ahlburg, Oliver Hergert, Peter G. Jones, Daniel B. Werz
Summary: A novel class of highly activated donor-acceptor cyclopropanes with a single vinylogous acceptor is presented. These moieties undergo cycloaddition reactions with various substrates to form carbo- and heterocycles. The stereochemical outcome can be controlled by the choice of catalyst. Mechanistic and kinetic experiments were conducted to explain the catalytic cycle and stereoselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Yong Xia, Xiaohua Liu, Xiaoming Feng
Summary: The donor-acceptor (D-A) cyclopropanes, due to the synergistic push-pull effect of vicinal electron-donating and electron-withdrawing groups, are recognized as powerful building blocks for generating polyfunctional reactive intermediates. Enantioselective reactions of D-A cyclopropanes provide an efficient approach to enantioenriched acyclic and cyclic compounds. Chiral Lewis/Bronsted acids, transition metals, and organocatalysts have been designed for such transformations, including ring-openings, annulations, and rearrangements.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Miranda M. Sroda, Friedrich Stricker, Julie A. Peterson, Alexandria Bernal, Javier Read de Alaniz
Summary: The study shows that the switching properties and concentration dependence of DASAs are influenced by solution-state dielectric and intermolecular interactions. DASAs with higher zwitterionic resonance contributions in the open form, such as first- and third-generation architectures, can have their switching kinetics controlled by ion concentration. On the other hand, DASAs with a less charge-separated open form, like second-generation architecture, are less affected by ion concentration. This highlights the importance of understanding the impact of solution properties on the design of photoswitching materials.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Stefano Nicolai, Jerome Waser
Summary: This study reports a Lewis acid catalyzed (4+3) annulative addition reaction for the efficient synthesis of densely substituted azepanes. The reaction achieved good yields and high diastereoselectivity under mild conditions using ytterbium triflate or copper triflate with a trisoxazoline ligand as the catalyst. The obtained cycloadducts were convenient substrates for further modifications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
David A. McLeod, Mathias Kirk Thogersen, Casper Larsen Barlose, Mette Louise Skipper, Erlaitz Basabe Obregon, Karl Anker Jorgensen
Summary: This study presents a novel enantioselective (8+3) cycloaddition reaction using a chiral bifunctional Bronsted base catalyst. The reaction leverages an anionic activation strategy and differs from typical Lewis-acid activation protocols. Experimental and computational results support the relevance of this reaction and its potential application in organic synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Ming Bao, Karlos Lopez, Raj Gurung, Hadi Arman, Michael P. Doyle
Summary: A highly enantioselective synthesis of chiral dihydro-3H-carbazole-2-carboxylate derivatives is achieved via a one-pot cascade reaction catalyzed by nickel(II) perchlorate hexahydrate and scandium(III) trifluoromethanesulfonate. The reaction proceeds under mild conditions and provides the desired products in high yields and enantioretention. Furthermore, these dihydro-3H-carbazole-2-carboxylates can be transformed into decarboxylated compounds through hydrolysis and decarboxylation under unexpectedly mild reaction conditions, giving moderate yields with high retention of enantiomeric purity.
Article
Chemistry, Multidisciplinary
Heinrich F. von Koeller, Peter G. Jones, Daniel B. Werz
Summary: A 1,3-carbocarbonation of 2-substituted cyclopropane 1,1-dicarboxylates was achieved by copper catalysis, introducing various carbon residues at the 1- and 3- position of the former three-membered ring. The ring-opening attack with a Grignard reagent proceeded smoothly, and the intermediate was converted to the final product by reaction with appropriate carbon-based electrophiles under basic conditions. Grignard reagents derived from sp(3)-, sp(2)-, and sp-hybridized carbon residues were successfully used as nucleophiles, while aliphatic bromides and EBX derivatives served as electrophiles for sp moieties.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Shiksha Deswal, Avishek Guin, Akkattu T. Biju
Summary: The use of benzotriazoles as nucleophilic triggers in the three-component Yb(OTf)(3)-catalyzed ring-opening 1,3-aminofunctionalization of donor-acceptor (D-A) cyclopropanes is described. The reaction yields 1,3-aminohalogenation products in up to 84% yield when N-halo succinimide (NXS) is used as the third component. Alkyl halides or Michael acceptors as the third components lead to the formation of 3,1-carboaminated products in up to 96% yield in a one-pot operation. Using Selectfluor as the electrophile, the reaction affords 1,3-aminofluorinated products in a 61% yield.
Article
Chemistry, Organic
S. Sina Hosseini, Aida Abdi, Ali Nikbakht, Hamid Reza Bijanzadeh, Frank Rominger, Daniel B. Werz, Saeed Balalaie
Summary: A novel ring-opening reaction of donor-acceptor cyclopropanes (DACs) through a one-pot three-component nucleophilic addition of amines, CS2, and DACs has been described. New gamma-dithiocarbamate dialkyl malonate skeletons were obtained in up to 97% yield.
Article
Chemistry, Physical
Ming Bao, Karlos Lopez, Raj Gurung, Hadi Arman, Michael P. Doyle
Summary: A highly enantioselective synthesis of chiral dihydro-3H-carbazole-2-carboxylate derivatives is achieved via a one-pot cyclopentannulation-rearrangement cascade reaction. The reaction is catalyzed by nickel(II) perchlorate hexahydrate and scandium(III) trifluoromethanesulfonate, and involves the use of 3-methylindole and non-racemic donor-acceptor cyclopropanes. The resulting products show high yields and enantioretention under mild reaction conditions, and further transformation into decarboxylated compounds can be achieved with moderate yields and high enantiomeric purity.
Article
Chemistry, Applied
Alexander Lipp, Shorouk O. Badir, Ryan Dykstra, Osvaldo Gutierrez, Gary A. Molander
Summary: A novel synthetic method for catalyst- and additive-free decarbonylative trifluoromethylthiolation of aldehyde feedstocks has been developed, driven by selective photoexcitation of electron donor-acceptor complexes. The mechanistic intricacies of this process have been elucidated through a combination of experimental efforts and high-level quantum mechanical calculations. This study highlights the importance of EDA complexation for efficient alkyl radical generation and product formation in photochemical reactions.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Meifeng Hou, Jiajun Li, Fucai Rao, Zuliang Chen, Yingjing Wei
Summary: In this study, the construction of N-heterocyclic eight-membered rings using Lu(OTf)(3) as a catalyst is reported. A formal [4+4] cycloaddition reaction of cyclobutane 1,1-diesters with anthranils was used to deliver oxa-bridged eight-membered heterocycles, providing a potential method for building complex azocine compounds.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Gwyndaf A. Oliver, Maximilian N. Loch, Andre U. Augustin, Pit Steinbach, Mohammed Sharique, Uttam K. Tambar, Peter G. Jones, Christoph Bannwarth, Daniel B. Werz
Summary: The paper presents rare examples of cycloadditions involving D-A cyclopropanes and cyclobutanes with N-sulfinylamines and a sulfur diimide, leading to the formation of five- and six-membered rings containing adjacent heteroatoms. A one-pot, two-step strategy is introduced for the formal insertion of HNSO2 into D-A cyclopropanes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Polymer Science
Alexis Emmerich, Constantin C. Daniliuc, Armido Studer
Summary: The stereospecific ionic ring-opening polymerization of various donor-acceptor cyclopropanes allows for the preparation of chiral polymers, with the potential for diverse applications by adjusting the substituents of the monomers.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Courtney A. DelPo, Saeed-Uz-Zaman Khan, Kyu Hyung Park, Bryan Kudisch, Barry P. Rand, Gregory D. Scholes
Summary: Enhanced delocalization is beneficial for absorbing molecules in organic solar cells, and polaritons offer exceptional delocalization that can improve the efficiency of bilayer organic photovoltaics by aiding in exciton delivery to the donor-acceptor interface. The decay of polaritons in bilayer cavities shows an additional pathway through charge transfer, indicating that the charge transfer from the polariton is fast enough to outcompete decay to the ground state.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Organic
Anne-Doriane Manick, Bruno Salgues, Jean-Luc Parrain, Elena Zaborova, Frederic Fages, Muriel Amatore, Laurent Commeiras
Review
Chemistry, Applied
Muhammad Idham Darussalam Mardjan, Atef Mayooufi, Jean-Luc Parrain, Jerome Thibonnet, Laurent Commeiras
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2020)
Article
Chemistry, Organic
Anthony Vivien, Alexandra Bartoli, Jean-Luc Parrain, Laurent Commeiras
TETRAHEDRON LETTERS
(2020)
Article
Chemistry, Multidisciplinary
Titouan Desrues, Jeremy Merad, Daniela Andrei, Jean-Marc Pons, Jean-Luc Parrain, Maurice Medebielle, Adrien Quintard, Cyril Bressy
Summary: This study reported an enantioselective organocatalyzed acylation of alpha,alpha-difluorohydrins using a commercially available chiral isothiourea, greatly improving the enantioselectivity of the kinetic resolution process through electrostatic fluorine-cation interactions. The method allows for the synthesis of various fluorinated alcohols with exquisite enantiocontrol, such as 4,4-difluoro-1,3-diols, as well as demonstrated compatibility between aromatic and fluorinated groups in providing enantioenriched adducts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Organic
Muriel Amatore, Jean-Luc Parrain, Laurent Commeiras
Summary: Alkyne surrogates have emerged as alternative substitution partners in organic synthesis, overcoming drawbacks associated with alkynes and offering new opportunities for the preparation of high value molecules.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Bruno Salgues, Rudraditya Sarkar, Muhammad Luthfi Fajri, Yatzil Alejandra Avalos-Quiroz, Anne-Doriane Manick, Michel Giorgi, Nicolas Vanthuyne, Yannick Carissan, Christine Videlot-Ackermann, Jorg Ackermann, Gabriel Canard, Jean-Luc Parrain, Boris Le Guennic, Denis Jacquemin, Muriel Amatore, Laurent Commeiras, Elena Zaborova, Frederic Fages
Summary: The novel di(benz[f]indenone)-fused tetraazaanthracene derivative synthesized in this study showed strong electron-accepting character, making it attractive for the generation of n-channel semiconducting materials. It exhibited electron transport in organic field effect transistors and demonstrated potential as an electron acceptor material in organic solar cells.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Milane Saidah, Muhammad Idham Darussalam Mardjan, Geraldine Masson, Jean-Luc Parrain, Laurent Commeiras
Summary: The first intermolecular organocatalytic enantioselective addition of indoles to prochiral 5-membered cyclic N-acyliminium ions, generated from 5-hydroxy-alpha,beta-unsaturated pyrrolidin-2-ones, is reported hereinafter. The reaction proceeds smoothly with a range of 5-hydroxy-5-substituted-alpha,beta-unsaturated pyrrolidin-2-ones and indoles using BINOL-derived phosphoric acid catalyst to afford alpha,beta-unsaturated lactams embedding a tetrasubstituted stereogenic center in high yields and enantioselectivities.
Article
Chemistry, Physical
D. Nikolaievskyi, M. Torregrosa, A. Merlen, S. Clair, O. Chuzel, J. -L Parrain, T. Neisus, A. Campos, M. Cabie, C. Martin, C. Pardanaud
Summary: This study demonstrates the detection of crumpling effects in Raman spectra using various types of graphene materials. The main finding is that these crumples enhance the intensity of the G band, similar to twisted bi-layer graphene. Surface defects created by crumples are included in the analysis, providing an updated understanding of point and linear defects. Additionally, the existence of 23 resonant additional bands at 633 nm is reported for the first time, attributed to edge modes formed by a high density of crumples. Raman plots are used to gain qualitative information about layer stacking.
Article
Chemistry, Applied
Kevin Masson, Maxime Dousset, Bohdan Biletskyi, Sara Chentouf, Jean-Valere Naubron, Jean-Luc Parrain, Laurent Commeiras, Paola Nava, Gaelle Chouraqui
Summary: An access to functionalised eight-membered carbocyclic ring compounds was developed by stirring an unusual vinylogous Donor-Acceptor Cyclopropane (DAC) in boiling o-xylene. Experimental and computational studies were conducted to explain the observed diastereoselectivity/regioselectivity transfer and provide mechanistic insights.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Review
Chemistry, Multidisciplinary
Amel Abdou-Mohamed, Clara Aupic, Corentin Fournet, Jean-Luc Parrain, Gaelle Chouraqui, Olivier Chuzel
Summary: Four-coordinate organoboron derivatives have interesting properties in chemistry, physics, biology, electronics, and optics. The synthesis of smart functional materials based on chiral organoboron compounds is in high demand, making the exploration of stereoselective synthesis of boron-stereogenic organo-derivatives desirable. However, the stereoselective construction of organoboron compounds stereogenic at boron has been less studied due to configurational stability concerns. Nowadays, configurationally stable compounds have been highlighted, showing the potential for stereoselective building of the four-coordinate boron center and encouraging future endeavors and developments in the field.
CHEMICAL SOCIETY REVIEWS
(2023)
Review
Chemistry, Multidisciplinary
Bohdan Biletskyi, Pierre Colonna, Kevin Masson, Jean-Luc Parrain, Laurent Commeiras, Gaelle Chouraqui
Summary: In this review, the release of ring strain in cyclobutane and cyclopropane derivatives is highlighted as a way to rapidly increase molecular complexity. The state-of-the-art of ring expansions involving three- and four-membered cycles is discussed, with an emphasis on reaction types and mechanisms. Selected examples are used to illustrate the synthetic potential of this elegant synthetic tool.
CHEMICAL SOCIETY REVIEWS
(2021)
Article
Chemistry, Inorganic & Nuclear
Marion Delorme, Alexander Punter, Raquel Oliveira, Corinne Aubert, Yannick Carissan, Jean-Luc Parrain, Muriel Amatore, Paola Nava, Laurent Commeiras
DALTON TRANSACTIONS
(2019)
Article
Chemistry, Multidisciplinary
Clara Aupic, Amel Abdou Mohamed, Carlotta Figliola, Paola Nava, Beatrice Tuccio, Gaelle Chouraqui, Jean-Luc Parrain, Olivier Chuzel
