Article
Chemistry, Applied
Tao Wang, Bo Huang, You-Qing Wang
Summary: Using chiral phosphoric acids as organocatalysts, a formal asymmetric (4+2) cycloaddition of 3-methylene isoindolinone and in situ-generated ortho-quinone methide substrates is achieved. This reaction allows the construction of spiro chroman-isoindolinones containing spiro-N,O-heterocycles with high enantioselectivity, with a broad substrate scope.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
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, Multidisciplinary
Wenyao Wang, Xiaoze Bao, Shiqiang Wei, Shah Nawaz, Jingping Qu, Baomin Wang
Summary: A catalytic asymmetric sequential annulation/aldol reaction of 4-isothiocyanato pyrazolones and allenyl ketones has been developed, leading to a series of spiro[pyrrole-pyrazolone] heterocycles and structurally novel spiro[thiopyranopyrrole-pyrazolone] derivatives in good yields with high to excellent enantioselectivities. The diversity of product structures was further enhanced by easy transformations.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Abhijit Manna, Harshit Joshi, Vinod K. Singh
Summary: A novel organocatalytic cascade approach has been developed for the synthesis of spiro-cyclopropyl oxindole derivatives. This methodology demonstrates remarkable stereocontrol, wide substrate scope, and scalability, and represents the first example of vinylogous Michael initiated ring closure reaction for the synthesis of chiral 3,3'-cyclopropyl oxindole.
JOURNAL OF ORGANIC CHEMISTRY
(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, Organic
Yue Ren, Wangyu Shi, Yi Tang, Shixiang Piao, Songcheng Yu, Yongjun Wu, Hongchao Guo
Summary: A series of gamma-substituted MBH carbonates were synthesized and reacted with electrophilic exocyclic alkenes through phosphine-catalyzed annulations, resulting in the formation of valuable spirocyclopentenes with moderate to excellent yields and diastereoselectivities. The annulation process tolerates a wide range of MBH carbonates with gamma-hydrogen, alkenyl, and alkynyl substituents. Notably, this annulation involves the beta, gamma, and delta carbons of MBH carbonates, which is unprecedented.
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
Tetsuya Ezawa, Yoshihiro Sohtome, Daisuke Hashizume, Masaya Adachi, Mai Akakabe, Hiroyuki Koshino, Mikiko Sodeoka
Summary: This study explores stereo-chemical dynamics in Ni(II)-catalyzed reactions, demonstrating a wide substrate scope and high selectivity in forming CN-containing building blocks with adjacent stereocenters. Computational investigations indicate that enantioselectivity is governed by the deprotonation process, while unique syn addition is controlled by noncovalent interactions between the nitrone and ligand.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Elisa Brambilla, Camilla Pozza, Silvia Rizzato, Giorgio Abbiati, Valentina Pirovano
Summary: This paper describes an enantioselective phosphine-catalyzed [3+2] cycloaddition reaction between aza-aurones and allenoates. The reaction proceeds under mild conditions and offers 2-spirocyclopentyl indolin-3-one derivatives as a single gamma-isomer with high stereocontrol.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Christoph Etling, Giada Tedesco, Markus Kalesse
Summary: This study investigated the different reactivity of trienones under Lewis and Bronsted acids catalysis, resulting in novel Nazarov cyclization tandem reactions terminating oxyallyl cations by ene-type reactions. The bicyclic spiro compounds produced were shown to be useful intermediates for further functionalization. Furthermore, the tandem Nazarov/ene cyclization was found to be preferred over a Nazarov/[3+2] tandem reaction for all substrates, regardless of chain length.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Tanno A. Schmidt, Stephan Schumann, Andreas Ostertag, Christof Sparr
Summary: In this study, we report the stereoselective synthesis of triptycyl sulfones with atropisomerism using a chiral phosphoric acid catalyst. The oxidation of a stereodynamic thioether controlled by the catalyst allowed selective access to enantioenriched triptycyl sulfoxides. Subsequent enantiospecific and diastereoselective catalytic oxidation resulted in overall control over the stereogenic C-S axis, with a stereoselectivity of up to (-sc): (+sc) : (ap)=94 : 6 :<1.
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, Organic
Lona Dutta, Anwita Chattopadhyay, Nisha Yadav, S. S. V. Ramasastry
Summary: This study presents a metal-free strategy for the synthesis of various alpha-arylidene cyclopenta[b]indoles by phosphine-catalysed (3 + 2) annulation of alpha,beta-ynones and 3-nitroindoles. The rearomatisation of the indole nucleus was observed for the first time during this annulative transformation. The method was also applied to the synthesis of an antimalarial natural product, bruceolline E.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Applied
You-Cai Wu, Bao-Dong Cui, Yan Long, Wen-Yong Han, Nan-Wei Wan, Wei-Cheng Yuan, Yong-Zheng Chen
Summary: The study demonstrates an asymmetric (4+1) annulation catalyzed by a chiral phosphoric acid, leading to the synthesis of a range of spiro[dihydrobenzofuran-2,3 '-oxindoles/2,4 '-oxisoquinoline] derivatives with excellent stereocontrol. The protocol showcases metal-free participation with heterocyclic diazo compounds as direct nucleophiles, offering a straightforward and efficient process for accessing structurally-diverse spiro-heterocyclic compounds.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
S. K. Abu Saleh, Atanu Hazra, Maya Shankar Singh, Saumen Hajra
Summary: This study demonstrates the use of Bronsted acid and/or Lewis acid catalysis for the selective C3-allylation and formal [3 + 2]-annulation reactions, leading to the direct synthesis of 3-allyl-3-aminomethyl oxindoles and 5-silyl methyl spiro[pyrrolidine-3,3'-oxindoles]. The reaction of nonracemic spiroaziridines with allyl-Grignard reagent under catalyst-free conditions also provides good stereoselectivity in the formation of 3-allyl-3-aminomethyl oxindoles (ee up to 80%). The allylation protocol is useful for the efficient synthesis of coerulescine and various 5'-substituted spiro[pyrrolidine-3,3'-oxindoles].
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Guillaume Arcile, Pascal Retailleau, Jamal Ouazzani, Jean-Francois Betzer
Summary: This study describes the first total synthesis of trienylfuranol A, a fungal metabolite, in 8 steps. The stereochemistry of the chiral center bearing the trienyl side chain was controlled by adding nucleophilic species on substituted gamma-butyrolactone, leading to the desired configuration. The use of Hantzsch ester as an organic hydride donor enabled the achievement of the desired stereochemistry.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(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, Medicinal
Tao Jia, Oumar Diane, Deepanjan Ghosh, Myriem Skander, Gaelle Fontaine, Pascal Retailleau, Joel Poupon, Jerome Bignon, Ytabelle Maga Moulai Siasia, Vincent Servajean, Nathalie Hue, Jean-Francois Betzer, Angela Marinetti, Sophie Bombard
Summary: This article introduces a new series of bimetallic platinum-(II) complexes with NHC-type bridging ligands, which exhibit cytotoxicity, cell accumulation, and DNA binding properties in cancerous cells. These complexes demonstrate significant radiosensitizing effects by inhibiting DNA repair mechanisms, leading to persistent accumulation of irradiation-induced DNA damages. This study provides the first in vitro evidence for the radiosensitizing properties of NHC-platinum complexes, suggesting their potential use in combined chemo-radiotherapy protocols.
JOURNAL OF MEDICINAL CHEMISTRY
(2023)
Article
Chemistry, Organic
Guillaume Arcile, Theo Massard, Elsa van Elslande, Jamal Ouazzani, Jean-Francois Betzer
Summary: A biomimetic-inspired synthesis of sporochartines A-D is described, which involves a [4 + 2] Diels-Alder cycloaddition reaction between (-)-sporothriolide and (+)-trienylfuranol A. The enantiopure total synthesis of (+)-trienylfuranol A is achieved for the first time, which contains an unusual and sensitive terminal trienyl moiety.
ORGANIC CHEMISTRY FRONTIERS
(2023)
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
Guillaume Arcile, Jamal Ouazzani, Jean-Francois Betzer
Summary: In this study, the first use of Zippertex technology in the Piancatelli rearrangement reaction under subcritical water conditions was described. This innovative approach efficiently transformed various bio-sourced furyl carbinols into cyclopentenone derivatives, avoiding the formation of side-products and polymeric materials.
REACTION CHEMISTRY & ENGINEERING
(2022)
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)
