Article
Chemistry, Multidisciplinary
Tom D. D'Arcy, Mark R. J. Elsegood, Benjamin R. Buckley
Summary: The highly enantioselective organocatalytic tandem o-HPD-[4+2] reaction described offers a practical method for the synthesis of complex scaffolds. This approach utilizes a chiral oxaziridinium organocatalyst to afford dearomatized products in high enantioselectivity, demonstrating its potential for gram-scale applications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Wei Liu, Tianren Qin, Wansen Xie, Xiaoyu Yang
Summary: Helicenes and helicene-like molecules with unique helical chirality have found wide applications in various research fields. However, the catalytic enantioselective synthesis of helicenes has been relatively underexplored. In the past two decades, significant progress has been made in this field, including methods enabled by both transition metal catalysis and organocatalysis.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Physical
Aleksandra Buchcic-Szychowska, Anna Zawisza, Stanislaw Lesniak, Michal Rachwalski
Summary: In this study, chiral aziridine-phosphines were used as catalysts in the asymmetric Morita-Baylis-Hillman reaction. The desired chiral products were obtained in moderate to high yields and with a high enantiomeric excess. The use of enantiomeric pairs of catalysts led to the formation of products with opposite absolute configurations.
Article
Chemistry, Organic
Baixue Liu, Peng Liu, Xue Wang, Feng Feng, Zhen Wang, Wenqiang Yang
Summary: A general method for the gram-scale enantioselective synthesis of P-stereogenic cyclic phosphine oxides has been developed using copper-catalyzed dynamic kinetic resolution, leading to high yields and high enantioselectivities. The resulting products can be easily reduced to obtain useful P(III)-stereogenic cyclic phosphines. A proposed mechanism involves the unusual rapid racemization of SPOs.
Article
Chemistry, Multidisciplinary
Daniel Moser, Kalipada Jana, Christof Sparr
Summary: In this study, the feasibility of atroposelective P-III/P-V=O redox organocatalysis by the Staudinger-aza-Wittig reaction is described. The formation of isoquinoline heterocycles allows for the synthesis of a wide range of valuable atropisomers with high enantioselectivities. The reaction is catalyzed by a chiral phosphine catalyst, with stereocontrol achieved through a silane reductant and Bronsted acid co-catalysis. The products can be easily transformed into N-oxides, naphthol, and triaryl phosphine variants, providing access to diverse aromatic heterocycles with precise control over their configuration.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Applied
Andreu Vidal-Albalat, Bruno Matos Paz
Summary: Flavonoids and cannabinoids have been extensively studied for their therapeutic potential in various diseases. Creative synthetic methodologies have been developed to overcome limitations in their synthesis. This review provides an overview of enantioselective organocatalytic strategies applied to the synthesis of flavonoids and cannabinoids to date.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Physical
Da Xu, Yu Chang, Yidong Liu, Wenling Qin, Hailong Yan
Summary: This study achieved the enantioselective construction of stable VQM intermediates through organocatalyzed bromination, and revealed the mechanistic details of the two sequential events in VQM-involved reactions. The high potential of VQM as axially chiral synthetic reagents in organic chemistry was demonstrated.
Article
Chemistry, Multidisciplinary
Chaoyang Li, Xinyue Niu, Wan Xu, Zhanwei Bu, Wenjing Zhang, Qilin Wang
Summary: This study presents an efficient catalyst-free strategy for skeletal editing of organophosphines through cleavage of P-Ar bonds and insertion of transformable propionates. It also demonstrates the synthesis of a range of novel compounds with high diastereoselectivity.
Article
Chemistry, Multidisciplinary
Binghui Wang, Yilin Liu, Chenyang Jiang, Zheng Cao, Shanshan Cao, Xiaowei Zhao, Xu Ban, Yanli Yin, Zhiyong Jiang
Summary: Describes a chiral Bronsted acid-catalysed asymmetric hydrophosphinylation of 2-vinylazaarenes by secondary phosphine oxides. P-chiral 2-azaaryl-ethylphosphine oxides are synthesized with high yields and ees, allowing for flexible modulation of substituents. The resulting P-chiral tertiary phosphines from the reduction are confirmed as effective C-1-symmetric chiral 1,5-hybrid P,N-ligands, making these adducts valuable in asymmetric metal catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Lucia Veltri, Roberta Amuso, Paola Vitale, Maria A. Chiacchio, Cinzia Benincasa, Bartolo Gabriele
Summary: A new process has been developed for the high value added conversion of carbon dioxide to 1,3-oxazine-2,4-diones through catalytic carboxylative heterocyclization of readily available 3-ynamides, yielding products in 44-85% yields under relatively mild conditions.
JOURNAL OF CO2 UTILIZATION
(2021)
Article
Chemistry, Multidisciplinary
Bastien Michelet, Agnes Martin-Mingot, Jean Rodriguez, Sebastien Thibaudeau, Damien Bonne
Summary: Since the pioneer reports of the groups of Akiyama and Terada, the field of Bronsted acid organocatalysis has been continuously growing with the development of ingenious strategies for the activation of challenging substrates. Different approaches such as superacidic organocatalysts and the combination of Lewis and Bronsted acids have emerged, highlighting the complementarity of these strategies.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Adrien Quintard
Summary: Selective copper catalysis activation of ketoacids, particularly bio-sourced 1,3-acetonedicarboxylic acid, and condensation with aldehydes under mild conditions, can lead to rapid preparation of natural product fragments and significant progress in this field through multicatalytic combination with organocatalysis. Additionally, cascade incorporation of fluorine offers new synthetic analogues with improved properties for a wide range of applications.
Article
Chemistry, Physical
Pilar Elias-Rodriguez, Ana T. Carmona, Antonio J. Moreno-Vargas, Inmaculada Robina
Summary: In this study, iminosugar derivatives containing a pyrrolidine-phosphine moiety were synthesized and used as catalysts in the [3 + 2] cycloaddition reaction between alkyl allenoates and electron-deficient imines. The results demonstrated that under appropriate conditions, 1,2,3,5-tetrasubstituted pyrrolines with high yields and good diastereoselectivities were obtained.
Article
Chemistry, Organic
Jie-Sheng Tian, Yu He, Zhi-Yuan Gao, Xu Liu, Shuang-Feng Dong, Peng Wu, Teck-Peng Loh
Summary: A metal-free, water-tolerant, one-pot process for ortho-acylation of phenols has been developed, promoted by the iodine source/hydrogen peroxide system. This transformation involves ether formation, iodocyclization, C-C bond cleavage, and oxidative hydrolysis in a one-step manner, as supported by control experiments.
Article
Chemistry, Applied
Marta Meazza, Ramon Rios
Summary: This study describes the first synthesis of 2-alkenylquinolines from 2-allylquinolines and alpha,beta-unsaturated aldehydes. The reaction exhibits high regioselectivity and enantioselectivity, with a broad tolerance of functionalities in both the enal aromatic ring and the quinoline.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Weiping Zhou, Arnaud Voituriez
Summary: An efficient and straightforward gold-catalyzed protocol has been developed for the synthesis of 2-substituted 4-oxo-4-arylbutanal derivatives, allowing for the facile synthesis of cycloalkyl-1-one compounds of different ring sizes. The methodology was also extended to the synthesis of tetrahydrocycloalkyl[b]pyrrole derivatives found in active pharmaceutical ingredients, with a mechanistic investigation revealing a [3,3]-sigmatropic rearrangement of a sulfonium intermediate in the process.
Review
Chemistry, Organic
Anthony J. Fernandes, Armen Panossian, Bastien Michelet, Agnes Martin-Mingot, Frederic R. Leroux, Sebastien Thibaudeau
Summary: The extraordinary instability of such an ion explains many peculiarities of organic reactions. Famous organic chemists have contributed greatly to the understanding of carbocations as reaction intermediates. While carbocations with electron-withdrawing groups remain transient species, they continue to be studied for their potential in synthetic transformations.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
David Augros, Corinne Comoy, Yves Fort, Frederic R. Leroux, Armen Panossian
Summary: This study investigates the challenging atropo-enantioselective coupling of in-situ generated arynes and aryllithiums in the presence of a chiral ligand of lithium for the first time. It demonstrates the feasibility of this concept, by affording enantioenriched axially chiral biaryls even in the case of products showing a high degree of steric congestion around the newly created aryl-aryl bond.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Applied
Charlotte Lorton, Antoine Roblin, Pascal Retailleau, Arnaud Voituriez
Summary: An enantioselective phosphine-catalyzed transformation has been developed for the synthesis of chiral cyclobutene triesters and fluorinated spirocyclic compounds. This catalytic methodology enables the synthesis of functionalized cyclobutenes and surprising reactivity for the synthesis of spiro-indenone products.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Weiping Zhou, Arnaud Voituriez
Summary: A cationic gold(I)-catalyzed asymmetric [3,3]-sigmatropic rearrangement of sulfonium leads to the formation of cyclopentenones with a C4-quaternary stereocenter after cyclization. This methodology was successfully applied to the efficient total synthesis of five natural sesquiterpenoids, demonstrating moderate to good yields and excellent enantiomeric excesses in 26 examples.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Zhenhao Zhang, Nazarii Sabat, Gilles Frison, Angela Marinetti, Xavier Guinchard
Summary: This study presents a new gold(I) catalyst for highly enantioselective multicomponent reactions between aldehydes, hydroxylamines, and cyclic yne-enones. The method shows broad applicability and achieves high yields, total diastereoselectivity, and high enantiomeric excess.
Article
Chemistry, Organic
Yunliang Yu, Nazarii Sabat, Meriem Daghmoum, Zhenhao Zhang, Pascal Retailleau, Gilles Frison, Angela Marinetti, Xavier Guinchard
Summary: Enantioselective tandem cycloisomerization/addition reactions of 2-alkynyl enones with 1- and 2-naphthols were investigated using gold(I) catalysts featuring hybrid phosphine-phosphoric acid chiral ligands, based on the tethered counterion-directed catalysis strategy. The reactions proceeded at low catalyst loading (0.2-1 mol%) without the need for silver additives, and the naphthols acted as both O- and C-nucleophiles, resulting in the formation of addition products with high enantioselectivity. The mechanism of these reactions was elucidated by DFT calculations.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Yunliang Yu, Zhenhao Zhang, Arnaud Voituriez, Nicolas Rabasso, Gilles Frison, Angela Marinetti, Xavier Guinchard
Summary: Stereocontrol in the enantioselective Au(i) catalyzed dearomatizations of 1-naphthols with allenamides is achieved through intramolecular ion-pairing between the chiral gold-tethered phosphate and an iminium unit, providing a rigid and well-defined chiral environment for the key electrophilic intermediate.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Nawel Goual, Lorenzo Casimiro, Vincent Delattre, Pascal Retailleau, Stephane Maisonneuve, Nicolas Bogliotti, Remi Metivier, Juan Xie, Angela Marinetti, Arnaud Voituriez
Summary: Dibenzotriazonines are disclosed as a new class of nine-membered cyclic azobenzenes with a nitrogen function in the saturated ring chain. These compounds exhibit preferred E-configuration, high bi-directional photoswitching, and good thermal stability in both E- and Z-forms.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Clement Cazorla, Lorenzo Casimiro, Tanzeel Arif, Claire Deo, Nawel Goual, Pascal Retailleau, Remi Metivier, Juan Xie, Arnaud Voituriez, Angela Marinetti, Nicolas Bogliotti
Summary: Diphosphines with azobenzene scaffolds and their corresponding bis-gold chloride complexes were prepared and characterized through photophysical, spectroscopic, and X-ray diffraction studies. DFT calculations provided additional information on their electronic, structural, and spectroscopic properties. Comparative investigations were conducted on compounds with different substitution patterns to analyze the effects on structural and spectroscopic properties.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Organic
Fanny Cacheux, Geraldine Le Goff, Jamal Ouazzani, Jerome Bignon, Pascal Retailleau, Angela Marinetti, Arnaud Voituriez, Jean-Francois Betzer
Summary: Substituted and non-symmetrical furan-2,5-dicarbinols were synthesized from hydroxymethylfurfural (HMF), a renewable raw material. The Piancatelli rearrangement of these compounds yielded cytotoxic cyclopentenone derivatives, which exhibited significant cytotoxicity against eight human tumor cell lines.
ORGANIC CHEMISTRY FRONTIERS
(2021)