Article
Chemistry, Organic
Eric Cots, Jeroen Rintjema, Fernando Bravo, Kilian Muniz
Summary: A previously unreported meso form of the catalysts was discovered during the upscaling process. A new scalable route was developed to prevent epimerization of the lactamide arms, leading to more effective and time-saving syntheses of the precatalysts. The catalysts obtained from these procedures have been utilized in published reactions, achieving the highest enantiomeric excess ever reported.
Article
Chemistry, Organic
Chenyang Wang, Peng Shi, Carsten Bolm
Summary: In this study, dichloro- and dibromomethane were utilized as halogen sources to convert NH-sulfoximines to N-halo derivatives, using an in situ formed sulfoximidoyl-containing hypervalent iodine reagent under visible light. The reactions were carried out in air without the need for catalysts or additives, and the products were obtained in good to excellent yields.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Applied
Andres Vazquez-Lopez, James E. Allen, Sarah E. Wengryniuk
Summary: A metal-free olefin diamination via a heterocyclic group transfer (HGT) reaction of I(III) N-HVI reagents has been reported, resulting in the synthesis of 3-aminopiperidines with high selectivity. The HGT strategy utilizes heteroarenes as oxidatively masked amine nucleophiles to produce (hetero)arylonium salt products, which can be easily isolated and further diversified. Mechanistic studies suggest that the 6-endo selectivity is attributed to the ring opening of an intermediate aziridinium ion.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Review
Chemistry, Multidisciplinary
Ravinder Kumar, Yugam Khanna, Parul Kaushik, Raj Kamal, Shiwani Khokhar
Summary: This review summarizes the impressive breakthroughs in organic synthesis, specifically the inter/intra-molecular vicinal diamination of alkenes with electron-rich or deficient nitrogen sources. These breakthroughs predominantly involve iodine-based reagents/catalysts, which have gained interest due to their flexibility, non-toxicity, and environmental friendliness, resulting in a wide variety of useful organic compounds. The information collected also highlights the role of catalyst, oxidant, substrate scope, synthetic applications, and their limitations, with proposed mechanistic pathways to determine key factors governing regioselectivity, enantioselectivity, and diastereoselectivity ratios.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Organic
Masaki Fujie, Kyohei Mizufune, Yoshihiro Nishimoto, Makoto Yasuda
Summary: In this study, the 1-fluoro-1-sulfonyloxylation of styrenes using a hypervalent iodine ArI(OAc)2 was reported. Regression analysis showed that the electron-withdrawing ability and steric factor of substituents on ArI(OAc)2 influenced the 1,1-heterodifunctionalization. Designed ArI(OAc)2 derivatives with o-{2,4-(CF3)2C6H3}- and p-NO2-substituents achieved high selectivity.
Article
Chemistry, Organic
Masaki Fujie, Kyohei Mizufune, Yoshihiro Nishimoto, Makoto Yasuda
Summary: A method for 1-fluoro-1-sulfonyloxylation of styrenes using Bu4NBF4, sulfonic acids, and hypervalent iodine ArI(OAc)(2) is reported. Regression analysis of substituents on ArI(OAc)(2) revealed that their electron-withdrawing ability and steric factor influence the 1,1-heterodifunctionalization. o-{2,4-(CF3)(2)C6H3}- and p-NO2-substituted ArI(OAc)(2) were designed by regression analysis to achieve high selectivity.
Article
Chemistry, Organic
Xiao-Jun Deng, Hui-Xia Liu, Lu-Wen Zhang, Guan-Yu Zhang, Zhi-Xiang Yu, Wei He
Summary: This study describes a room-temperature metal-free iodoarene-catalyzed oxyamination of unactivated alkenes, resulting in the difunctionalization of alkenes by oxygen and nitrogen, leading to the synthesis of important 5-imino-2-tetrahydrofuranyl methanamine derivatives for drug development and biological studies. The mechanism involves activation of substrate alkene by a cationic iodonium(III) intermediate, followed by attack of oxygen atom from amides to form a five-membered ring intermediate, which then undergoes an S(N)2 reaction by NTs2 to give the final product. Promising results were also obtained for some substrates using chiral iodoarenes as catalysts in an asymmetric variant of this alkene oxyamination.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Abhaya Kumar Mishra, Romain Tessier, Durga Prasad Hari, Jerome Waser
Summary: In this study, functionalization of cysteine residues with lipophilic alkynes using amphiphilic ethynylbenziodoxolone reagents (EBXs) was successfully achieved under physiological conditions without the need for organic co-solvent or removal of oxygen. The transformation led to a significant increase of peptide lipophilicity and worked for various thiol-containing compounds and peptides of different lengths. His(6)-Cys-Ubiquitin was also alkynylated under these conditions, demonstrating the versatility of this method.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Mohamed Elsherbini, Wesley J. Moran
Summary: A simple catalytic electrosynthetic protocol utilizing hypervalent iodine reagents has been developed for oxidative transformations. The protocol eliminates the need for chemical oxidants and electrolytic salts, utilizing electricity to drive the iodine(I)/iodine(III) catalytic cycle. The method has been successfully validated with two different transformations and features a wide substrate scope, excellent functional group tolerance, and easy scale-up and catalyst recovery.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Mohamed Elsherbini, Wesley J. Moran
Summary: A simple catalytic electrosynthetic protocol for oxidative transformations mediated by hypervalent iodine reagents has been developed. This protocol eliminates chemical oxidants and their associated chemical waste by utilizing electricity to drive the catalytic cycle. It has been validated through two different hypervalent iodine-mediated transformations, showing wide substrate scope, excellent functional group tolerance, and the ability for scale-up and catalyst recovery.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Adriano Bauer, Nuno Maulide
Summary: This perspective article discusses the structural features of iodine(iii) compounds and their use as umpolung reagents, focusing on their ability to selectively couple two nucleophilic species via 2e(-) oxidation.
Article
Chemistry, Multidisciplinary
Jiang Nan, Xin Ren, Qiang Yan, Shilei Liu, Jing Wang, Yangmin Ma, Michal Szostak
Summary: A novel hypervalent iodine-induced twofold oxidative coupling of amines with amides and thioamides has been established, which chemoselectively assembles oxazoles and thiazoles. The mechanism involves the generation of ureas and thioureas as intermediates. These findings open up new avenues for exploring oxidative bond chemistry of amides and thioamides.
Article
Chemistry, Multidisciplinary
Xiao-Guang Yang, Feng-Huan Du, Jun-Jie Li, Chi Zhang
Summary: A practical method for dehydroxyazidation of alcohols using PPh3 and hypervalent azido-iodine(III) reagents is reported. The method allows for the late-stage azidation of structurally complex alcohols and the synthesis of the antiepileptic drug rufinamide.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Shiyong Peng, Jieyin He, Liangliang Yang, Hong Zhang, Hongguang Li, Ming Lang, Chao Chen, Jian Wang
Summary: A phenyliodine(III) diacetate-promoted dearomative spirocyclization of phenolic ketones was controlled by 1,1,1,3,3,3-hexafluoroisopropanol to provide two libraries of structurally interesting compounds, spirocyclohexadienonic ketals and their acetoxylated counterparts, in moderate to excellent yields. Control experiments revealed that the reaction proceeds through a spirocyclohexadienone-oxocarbenium cation species.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Joanna A. Jaszczewska-Adamczak, Jacek Mlynarski
Summary: Utilizing chiral dinuclear magnesium complexes for epoxidation reactions allows for efficient and highly selective synthesis of enantioenriched oxiranes, providing a new possibility for asymmetric synthesis.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Alexandra E. Bosnidou, Thomas Duhamel, Kilian Muniz
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Inorganic & Nuclear
Cristina Maquilon, Bart Limburg, Victor Laserna, Diego Garay-Ruiz, Joan Gonzalez-Fabra, Caries Bo, Marta Martinez Belmonte, Eduardo C. Escudero-Adan, Arjan W. Kleij
Article
Chemistry, Multidisciplinary
Luis Gutierrez, Suvendu Sekhar Mondal, Alberto Bucci, Noufal Kandoth, Eduardo C. Escudero-Adan, Alexandr Shafir, Julio Lloret-Fillol
Article
Chemistry, Multidisciplinary
Jose A. Souto, Federica Sarno, Angela Nebbioso, Chiara Papulino, Rosana Alvarez, Jessica Lombino, Ugo Perricone, Alessandro Padova, Lucia Altucci, Angel R. de Lera
FRONTIERS IN CHEMISTRY
(2020)
Article
Chemistry, Organic
Eric Cots, Jeroen Rintjema, Fernando Bravo, Kilian Muniz
Summary: A previously unreported meso form of the catalysts was discovered during the upscaling process. A new scalable route was developed to prevent epimerization of the lactamide arms, leading to more effective and time-saving syntheses of the precatalysts. The catalysts obtained from these procedures have been utilized in published reactions, achieving the highest enantiomeric excess ever reported.
Article
Chemistry, Organic
Jose A. Souto, David Roman, Marta Dominguez, Angel R. de Lera
Summary: In the synthesis of cyclodepsipeptide natural product alotamide A, intramolecular Csp(2)-Csp(2) Stille cross-coupling and macrolactam formation were identified as reliable protocols for constructing the alotamide A skeleton.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Jose A. Souto
Summary: A continuous flow synthetic protocol was described for the preparation of benzotropolones, and their derivatization to yield an inhibitor of (JmjC)-containing domain enzymes. The procedure proved to be efficient and reproducible, paving the way for the preparation of larger amounts of the product for more extensive biological studies.
Article
Chemistry, Multidisciplinary
Chang Qiao, Wangyu Shi, Arianna Brandolese, Jordi Benet-Buchholz, Eduardo C. Escudero-Adan, Arjan W. Kleij
Summary: A new catalytic route has been developed for the coupling of epoxides and CO2 to produce polymerizable six-membered bicyclic carbonates. By utilizing cyclic epoxides with a beta-positioned OH group, structurally diverse bicyclic cyclic carbonates can be obtained with good yields and high selectivity. The difference in reactivity between syn- and anti-configured epoxy alcohols is the key to achieve chemo-selectivity, with the anti-isomer leading to the formation of six-membered ring carbonates in the presence of a binary Al-III aminotriphenolate complex/DIPEA catalyst.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Jose Maria Munoz-Molina, Daniel Bafaluy, Ignacio Funes-Ardoiz, Adiran de Aguirre, Feliu Maseras, Tomas R. Belderrain, Pedro J. Perez, Kilian Muniz
Summary: In this study, we report a new method for the synthesis of pyrrolidines and piperidines via intramolecular C-H amination, and investigate the mechanistic pathway, revealing a key fluorinated copper(II) complex. The effects of catalyst ligand and substrate halide were explored from experimental and computational perspectives.
Article
Business
Jose Ari Povoas Souto Filho, Alberto Casado Lordsleem Junior, Joaquin Humberto Aquino Rocha
Summary: The study evaluated the application of lean construction principles and practices in construction companies in the Metropolitan Region of Recife, with Company 01 showing a consolidated lean management system ready to reap more benefits, Company 02 having difficulties in maintaining the philosophy, and Company 03 possessing lean knowledge but not yet stable.
REVISTA DE GESTAO E PROJETOS
(2022)
Article
Chemistry, Multidisciplinary
Xuetong Li, Jordi Benet-Buchholz, Eduardo C. Escudero-Adan, Arjan W. Kleij
Summary: A conceptually novel catalytic domino approach is presented for the synthesis of highly functional 1,4-dihydro-2H-1,3-benzoxazine-2-one derivatives. The chemoselectivity is achieved through a proper design of the precursor and the use of Thorpe-Ingold effects. The synthetic diversity of these CO2-based heterocycles is demonstrated, and an unusual ring-expansion sequence is observed from an alpha-alkylidene, five-membered cyclic carbonate to a six-membered cyclic carbamate by N-induced isomerization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Biochemistry & Molecular Biology
Mabel Catalan, Vicente Castro-Castillo, Javier Gajardo-de la Fuente, Jocelyn Aguilera, Jorge Ferreira, Ricardo Ramires-Fernandez, Ivonne Olmedo, Alfredo Molina-Berrios, Charlotte Palominos, Marcelo Valencia, Marta Dominguez, Jose A. Souto, Jose A. Jara
RSC MEDICINAL CHEMISTRY
(2020)
Letter
Chemistry, Organic
Alexandra E. Bosnidou, Thomas Duhamel, Kilian Muniz
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Angel Garcia-Raso, Angel Terron, Yannick Rosello, Antonio Frontera, Oscar Castillo, Garikoitz Beobide, Sonia Perez-Yanez, Eduardo C. Escudero-Adan, Juan J. Fiol
Article
Chemistry, Multidisciplinary
Luis Escobar, David Villaron, Eduardo C. Escudero-Adan, Pablo Ballester
CHEMICAL COMMUNICATIONS
(2019)
