Article
Chemistry, Organic
Jiagen Li, Ming Wang, Xuefeng Jiang
Summary: Stereoselective thioglycosylation via palladium-catalyzed allylic rearrangement was successfully achieved in this study, yielding various substituents on alpha-isomer thioglycosides. Additionally, a comprehensive series of aryl and benzyl thioglycosides were obtained through a combination of thiosulfates with glycals derived from different carbohydrates.
Article
Chemistry, Multidisciplinary
Zhipeng Zheng, Youge Pu, Javier Adrio, Patrick J. Walsh
Summary: This study reports a synthetic method for trans-aziridines using imines and benzylic or alkyl halides with sulfenate anions (PhSO-) as catalysts. The method shows broad applicability and good diastereoselectivity, and can be used with substrates bearing heterocyclic aromatic groups, alkyl, and electron-rich and electron-poor aryl groups. Ring-opening reactions further allow functionalization of aziridines containing cyclopropyl or cyclobutyl groups.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Juba Ghouilem, Christine Tran, Nicolas Grimblat, Pascal Retailleau, Mouad Alami, Vincent Gandon, Samir Messaoudi
Summary: This study presents a novel Pd-catalyzed reaction for anomeric C-H bond activation, leading to the synthesis of elusive C-(hetero)aryl glycosides with exclusive α-selectivity.
Article
Chemistry, Multidisciplinary
Zhen-Kai Wang, Yong-Jie Wu, Qi-Jun Yao, Bing-Feng Shi
Summary: We reported a highly enantioselective synthesis of chiral DAMAs via cobalt-catalyzed enantioselective C-H alkoxylation strategy. The reaction features easy operation, the use of earth-abundant and cost-efficient cobalt(II) catalyst, and readily available ligand. A range of chiral DAMAs were efficiently synthesized in high yields with excellent enantioselectivities (up to 90 % yield and up to 99 % ee) through desymmetrization and parallel kinetic resolution. Moreover, this protocol was also compatible with the synthesis of chiral benzylamines via kinetic resolution.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Ming-Kuan Wang, Yun-Cheng Luo, Hai-Yang Zhao, Yanxia Zhang, Dawei Zhang, Xingang Zhang
Summary: A cobalt-catalyzed trans-selective arylfluoroalkylation of cyclopentenes has been developed for the efficient synthesis of polysubstituted cyclopentanes. The reaction exhibits broad substrate scope, high functional group tolerance, and synthetic convenience.
Article
Chemistry, Organic
Changpeng Chen, Zhijun Wang, Sha Wang, Liang Xu, Xiaoming Zeng
Summary: We describe the selective cyclization of anilines with cyclobutanones and congeners using chromium catalysis. This reaction enables the formation of diastereoselective tetrahydroquinolines by linking two strained four-membered rings, leading to the synthesis of cyclobutane-fused and constrained spirotetrahydroquinolines (STHQs) and complex multiple spiro carbon-containing polyazacycles. The constrained STHQs have been utilized as versatile precursors for the synthesis of oxygen-, nitrogen-, and thio-substituted spiro analogues, as well as dioxygen-incorporated spiroazacycles.
Article
Chemistry, Organic
Arne G. A. Geissler, Jasmin R. Riesterer, Bernhard Breit
Summary: The intramolecular addition of tosylureas to allenes is highly diastereoselective with palladium or rhodium catalysis, yielding 1,3-cyclic ureas. Palladium catalysis allows access to thermodynamic anti-tetrahydropyrimidinones, while rhodium catalysis enables synthesis of kinetic syn-tetrahydropyrimidinones, both with excellent yields and diastereoselectivities. The obtained tetrahydropyrimidinones are easily deprotected and modified, demonstrating their synthetic value.
Article
Chemistry, Multidisciplinary
Tingting Li, Gerald B. Hammond, Bo Xu
Summary: A widely applicable approach to synthesize ketones, esters, and amides via the oxidative C-C bond cleavage of readily available alkyl aldehydes has been developed using green and abundant molecular oxygen as the oxidant, and base metals (cobalt and copper) as catalysts. This strategy can be extended to the one-pot synthesis of ketones from primary alcohols and alpha-ketoamides from aldehydes.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Yong-Jie Wu, Zhen-Kai Wang, Zhen-Sheng Jia, Jia-Hao Chen, Fan-Rui Huang, Bei-Bei Zhan, Qi-Jun Yao, Bing-Feng Shi
Summary: A highly efficient synthesis of axially chiral biaryl amines through cobalt-catalyzed atroposelective C-H arylation using accessible cobalt(II) salt and salicyloxazoline ligand has been reported. This methodology provides a straightforward and sustainable access to a wide range of enantioenriched biaryl-2-amines with high yields (up to 99%) and excellent enantioselectivities (up to 99% ee). The scalability and diverse transformations highlight the synthetic utility of this unprecedented method.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yong-Jie Wu, Zhen-Kai Wang, Zhen-Sheng Jia, Jia-Hao Chen, Fan-Rui Huang, Bei-Bei Zhan, Qi-Jun Yao, Bing-Feng Shi
Summary: A highly efficient method for the synthesis of axially chiral biaryl amines through cobalt-catalyzed atroposelective C-H arylation has been reported. The method utilizes easily accessible cobalt(II) salt and salicyloxazoline ligand, and provides a straightforward and sustainable access to enantioenriched products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Luis Tarifa, M. Pilar del Rio, Laura Asensio, Jose A. Lopez, Miguel A. Ciriano, Ana M. Geer, Cristina Tejel
Summary: A straightforward catalytic method for the synthesis of complex C-substituted piperazines has been developed based on an uncommon head-to-head coupling of easily prepared imines. This efficient process allows the selective formation of a sole diastereoisomer, exhibits a broad substrate scope, and shows good functional group tolerance using a bench-stable iridium catalyst under mild reaction conditions. The addition of N-oxides notably enhances the catalytic activity and selectivity.
Article
Chemistry, Multidisciplinary
Leiyang Bai, Yinhao Ma, Xuefeng Jiang
Summary: Through a one-step catalytic operation, this study successfully designed a synthetic pathway for the total synthesis of isocalycanthine and its derivatives, which possess novel structures and alkaloid activities in dimeric cyclotryptamine alkaloids.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Applied
Yoshikazu Horino, Mayo Ishibashi, Juri Sakamoto, Miki Murakami, Toshinobu Korenaga
Summary: The diastereoselective synthesis of anti-homoallylic alcohols bearing conjugated (Z)-enynes through a palladium-catalyzed three-component reaction is described, featuring a broad substrate scope, good functional group compatibility, and high levels of (Z)-alkene stereocontrol. The reaction involves Pd(0) functioning as a catalyst in two fundamental steps: the generation of a borylated pi-allylpalladium species inducing umpolung allylation of aldehydes, and C(sp(2))-C(sp) cross-coupling. Further transformations of the obtained products highlight their synthetic utility.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Fei Wang, Yoshihiro Nishimoto, Makoto Yasuda
Summary: We report a method for formal carbon-carbon bond insertion using Lewis acid catalysts to react secondary benzylic halides with alpha-diazo esters, and the mechanism of this insertion is revealed. This reaction is applicable to various reactants and also achieves ring expansion.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Bing-Jie Wang, Guo-Xiong Xu, Zong-Wei Huang, Xu Wu, Xin Hong, Qi-Jun Yao, Bing-Feng Shi
Summary: We have developed a single-step method for constructing atropisomers with vicinal chiral axes, achieving good stereocontrol. The produced products exhibit circular polarized luminescence properties and are suitable for potential applications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Nicolas Gillaizeau-Simonian, Etienne Barde, Amandine Guerinot, Janine Cossy
Summary: A cobalt-catalyzed reaction method with high chemoselectivity was developed for the preparation of alpha-aryl amides with various functional groups. This method was successfully applied to the synthesis of alkaloids. Mechanistic studies suggest a radical process.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Review
Chemistry, Medicinal
Guillaume Masson, Domingo Gomez Pardo, Janine Cossy
Summary: This microreview focuses on the nucleophilic ring-opening of azetidiniums with various substitution patterns at C2, C3, and C4. The reactions often exhibit stereoselectivity and regioselectivity, leading to functionalized linear amines. Experimental selectivities correlated with Density Functional Theory (DFT) calculations provide insights into the factors governing regioselectivity.
Article
Chemistry, Organic
Andrea Zanetti, Geoffrey Schwertz, Marllon Nascimento de Oliveira, Mario Andres Gomez Fernandez, Zacharias Amara, Janine Cossy
Summary: A regioselective Pd-catalyzed allylic oxidation of amorphadiene, a key precursor to artemisinin, is described, which can substitute P450 enzymes in artemisinin biosynthesis and enhance the value of waste in the industrial semisynthetic process.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Mario Andres Gomez Fernandez, Marllon Nascimento de Oliveira, Andrea Zanetti, Geoffrey Schwertz, Janine Cossy, Zacharias Amara
Summary: A new method for the preparation of artemisinin was reported based on selective photochemical hydrothiolation of amorphadiene. Two distinctive activation pathways were discovered under solvent-free conditions or using a photocatalyst promoting H-abstraction. The key intermediate dihydroartemisinic aldehyde in the synthesis of artemisinin was obtained through chemoselective oxidation of the photochemically generated thioether followed by Pummerer rearrangement.
Review
Chemistry, Physical
Youssef Nassar, Fabien Rodier, Vincent Ferey, Janine Cossy
Summary: This review discusses the scope and limitations of stereoselective transformation of ketones to substituted olefins using first-row transition metal-catalyzed cross-couplings with various Grignard and zinc reagents.
Article
Chemistry, Multidisciplinary
Peter Polak, Janine Cossy
Summary: Good yields of 2-C-glycals and 2-C-ribals were achieved through a nickel-catalyzed cross-coupling reaction between 2-iodoglycals and 2-iodoribals using Grignard reagents. The synthesized compounds were further transformed into 2-C-2-deoxyglycosides, 2-C-diglycosides, and 2'-C-2'-deoxynucleosides. This method was successfully applied to the synthesis of a 2-chloroadenine 2'-deoxyribonucleoside, an important analogue of cladribine and clofarabine used in the treatment of multiple sclerosis and hairy cell leukemia.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Tomas J. Saiegh, Christophe Meyer, Janine Cossy
Summary: Hydroxamates derived from 3-sulfolene-3-carboxylic acid can undergo intra- and intermolecular rhodium(III)-catalyzed heteroannulations, involving C(sp(2))-H bond activation. These reactions provide a direct route to diversely substituted pyridones and pyridines fused to a sulfolene ring. The subsequent cheletropic elimination under microwave irradiation leads to the generation of pyridine ortho-quinodimethanes.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Thomas Abegg, Janine Cossy, Christophe Meyer
Summary: cis-1,2-Dialkenylcyclopropanes with a vinyl azide group were generated by Knoevenagel condensations and underwent cascade Cope and Winstein [3,3]-sigmatropic rearrangements under mild conditions. This reaction sequence allows for the synthesis of diversely substituted 1,4-cycloheptadienes with a secondary allylic azide containing up to three stereocenters.
Article
Chemistry, Organic
Peter Polak, Janine Cossy
Summary: This study reports the synthesis of 2-C-substituted 5-deoxyglucals from D-ribose using a nickel-catalyzed cross-coupling reaction. The obtained compounds were further transformed into 2-C-substituted 5-deoxyglycosides and 2-C-substituted 5-deoxynucleosides. The work also involves the reassignment of previously published structures.
Article
Chemistry, Organic
Janine Cossy
Summary: Due to advancements in techniques and technologies, biocatalysts are increasingly important in the field of chemistry. They have transitioned from being used on a laboratory scale to an industrial scale, allowing for efficient synthesis of complex molecules. Biocatalysis opens new areas of research and addresses challenges that traditional chemistry struggles with in terms of chemoselectivity and efficiency.
Article
Chemistry, Organic
Paul C. Ruer, Youssef Nassar, Peter Polak, Janine Cossy
Summary: Five-membered exo-glycals were synthesized from six-membered 2-iodo-endo-glycals through a metal/halogen exchange/ring-opening sequence followed by a cyclization catalyzed by Ag2CO3.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Elias Abedelnour, Stephanie Ognier, Olivier Venier, Laurent Schio, Michael Tatoulian, Janine Cossy
Summary: This study presents the direct synthesis of trifluoromethyl N,N-aminals from nitrogen containing heterocycles using argon plasma in a continuous flow microreactor without any additives or metal catalysts. The transformation of these compounds to N-trifluoroethyl amines is also reported.
CHEMICAL COMMUNICATIONS
(2023)
Review
Chemistry, Organic
Tomohiro Yasukawa, Katja S. Haheim, Janine Cossy
Summary: This article introduces the synthesis of 1,3-disubstituted bicyclo[1.1.1]pentanes (BCPs) by forming a C-C bond through cross-coupling reactions using transition metal catalysts. Two main strategies are described to obtain these compounds from nucleophilic BCPs or electrophilic BCPs, including relevant mechanisms.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Review
Chemistry, Organic
Janine Cossy, Peter Polak, Paul C. Ruer
Summary: This review focuses on the incorporation of a cyclobutyl substituent in molecules by transition metal-catalyzed cross-coupling, specifically the formation of C-C bonds. Three main strategies are discussed, involving electrophilic or nucleophilic cyclobutane derivatives.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Elias Abedelnour, Stephanie Ognier, Mengxue Zhang, Laurent Schio, Olivier Venier, Janine Cossy, Michael Tatoulian
Summary: The direct N-acylation of amines by esters in a microreactor using argon plasma is presented, resulting in high yields of amides.
CHEMICAL COMMUNICATIONS
(2022)