Article
Chemistry, Multidisciplinary
Oleg O. Shyshkov, Alexander A. Kolomeitsev, Berthold Hoge, Enno Lork, Axel Haupt, Mira Kessler, Gerd-Volker Roeschenthaler
Summary: Phosphoranides are hypervalent species that can serve as model compounds for intermediates or transition states in nucleophilic substitution reactions. This study reports the syntheses and properties of stable trifluoromethylphosphoranide salts, and investigates their reactivity towards electrophiles. The structures and dynamics of these compounds are determined using X-ray crystallography and NMR spectroscopy.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Thibaut Duhail, Jorna Kalim, Jerome Marrot, Bruce Pegot, Emmanuel Magnier, Elsa Anselmi
Summary: This study describes hypervalent iodine compounds with specific ligands, investigating the influence of these groups on the stability of cyclic structure and highlighting the crucial role of the trifluoromethyl chain as an efficient ligand. The structure and reactivity of the new skeletons are discussed in detail.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Junjie Yang, Yung-Yin Chan, Weida Feng, Ying-Lung Steve Tse, Ying-Yeung Yeung
Summary: Electrophilic halogenation reactions are commonly used in various areas. N-Haloamides are frequently employed as halogen sources, but their activation is often achieved with Lewis basic chalcogens as catalysts. However, the resulting intermediate is sensitive to moisture and nucleophiles, limiting its compatibility in some reactions. This study introduces a highly efficient catalytic halogenation protocol using phenyl selenium with ortho-substituted carboxylic acid as the catalyst, which demonstrates improved stability and applicability in various electrophilic functionalization reactions.
Article
Chemistry, Multidisciplinary
Lei Zhang, Wangzhen Bao, Yuchen Liang, Wenjing Pan, Dongyang Li, Lichun Kong, Zhi-Xiang Wang, Bo Peng
Summary: This study demonstrates the reversal of stereoselectivity in MBH-type [3,3]-rearrangement by using a new pair of rearrangement partners, leading to the synthesis of different types of alpha-aryl alpha,beta-unsaturated carbonyl derivatives. Mechanistic studies provide insights into the reaction pathway and the opposite stereoselectivities observed.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Matic Lozinsek, Helene P. A. Mercier, Gary J. Schrobilgen
Summary: The coordination chemistry of KrF2 is limited compared to XeF2, but in this study, new mixed krypton/xenon compounds were synthesized where KrF2 acts as a ligand coordinating to xenon atoms. This extends the XeF2-KrF2 analogy and introduces a new class of coordination compound.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Xia Wang, Peng Yang, Bo Hu, Qian Zhang, Dong Li
Summary: A novel transformation of primary amides to secondary amides was developed using hypervalent iodine reagents, promoting a Hofmann-type rearrangement to generate an isocyanate intermediate which was then trapped by a carboxylic acid from the same reagent to provide the corresponding secondary amides. This method not only offers an easy and efficient route for synthesizing secondary amides from primary amides, but also reveals novel reactivities of hypervalent iodine reagents.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Jef R. Vanhoof, Pieter J. De Smedt, Jan Derhaeg, Rob Ameloot, Dirk E. De Vos
Summary: A highly efficient electrocatalytic method for 1,2-dioxygenation of alkenes using readily available materials under ambient conditions is developed, showing broad applicability and excellent yields.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Organic
Yang Zhifang, Cheng Yifu, Zhang Beibei, Dong Yunyi, Han Chi, Du Yunfei
Summary: This review discusses the development and application of hypervalent-iodine chemistry, with a focus on oxidative rearrangement reactions catalyzed by hypervalent iodine reagents. These reactions have wide application prospects and are of great significance to the field of organic research.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jessica Neufeld, Constantin. G. G. Daniliuc, Ryan Gilmour
Summary: This study presents a regioselective fluorocyclisation of beta,gamma-unsaturated oximes through I(I)/I(III) catalysis, using p-iodotoluene as a cost-effective catalyst, Selectfluor((R)) as the oxidant, and an amine.HF complex as the fluoride and Bronsted acid source. The transformation produces 5-fluoromethylated isoxazolines, with a range of aliphatic and aromatic systems yielding up to 56%.
HELVETICA CHIMICA ACTA
(2023)
Review
Chemistry, Applied
Yun Xing, Chen Li, Jianping Meng, Zhen Zhang, Xin Wang, Zhichuan Wang, Yong Ye, Kai Sun
Summary: Allyl alcohol compounds are widely used as structural units for synthesizing important carbonyl compounds through migration rearrangement reactions, but the research is still in exploratory stages and lacks a comprehensive review summarizing significant advances in this field.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Zexian Li, Minyan Wang, Zhuangzhi Shi
Summary: An efficient method for photocatalytic perfluoroalkylation of vinyl-substituted all-carbon quaternary centers involving 1,2-aryl migration has been developed, generating valuable multisubstituted perfluoroalkylated compounds in a single step. Mechanistically, photoinduced alkyl radical addition to an alkene leads to migration of a vicinal aryl substituent from its adjacent all-carbon quaternary center, followed by generation of a C-radical bearing two electron-withdrawing groups and reduction by a hydrogen donor to complete the domino sequence.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Maxime Artault, Thomas Cantin, Melissa Longuet, Kassandra Vitse, Christ Daniel Matatu Mbengo, Frederic Guegan, Bastien Michelet, Agnes Martin-Mingot, Sebastien Thibaudeau
Summary: This study reports a method to reorganize the core structure of aliphatic unsaturated nitrogen-containing substrates by exploiting polyprotonation in superacid solutions. The superelectrophilic activation of N-isopropyl systems allows for the selective functionalization of nitrogen-containing substrates. It is demonstrated that this skeletal reorganization can be controlled through protonation interplay.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Zhongxue Fang, Yiming Ma, Shaopeng Liu, Huricha Bai, Shuang Li, Yongquan Ning, Giuseppe Zanoni, Zhaohong Liu
Summary: The first successful synthesis of a wide range of cyclic 1,4-cycloheptadienes with high yields and predictable stereochemistry has been achieved using easily decomposable alkenyl-N-triftosylhydrazones. This reaction enables the formation of bridged and fused polycyclic systems, as well as the natural product dictyopterene C ' and its isomer ectocarpene.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Wen Liu, Shuya Xing, Shao-Fei Ni, Cheng Ma, Qiujin Fan, Zhiyong Ye, Yanchuang Zhao, Ting Ouyang, Ying Bai, Xinxin Shao
Summary: In this research, a Lewis base-catalyzed trifluoromethylsulfinylation of alkyl alcohols and phenols was achieved using a stable electrophilic trifluoromethylsulfinylating reagent, resulting in the modular synthesis of various trifluoromethanesulfinate esters. This metal-free and catalytic transformation displayed broad functional group compatibility, enabling the late-stage modification of complex molecules and allowing the reuse of the phthalimide reagent. Notably, the reaction of 1-indanol led to the formation of alkenes, suggesting an intriguing mechanistic pathway involving O-trifluoromethylsulfinylation and subsequent elimination.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Koji Morimoto, Kana Yanase, Tetsuya Kajimoto, Yasuyuki Kita
Summary: A method using hypervalent iodine reagents for oxidative glycosylation was discovered, resulting in the synthesis of sugars of different sizes, providing new possibilities for further research.
Article
Chemistry, Multidisciplinary
Miguel A. Cortes Gonzalez, Patrik Nordeman, Antonio Bermejo Gomez, Denise N. Meyer, Gunnar Antoni, Magnus Schou, Kalman J. Szabo
CHEMICAL COMMUNICATIONS
(2018)
Article
Chemistry, Physical
Soumitra Agasti, Bhaskar Mondal, Tapas Kumar Achar, Soumya Kumar Sinha, Anjana Sarala Suseelan, Kalman J. Szabo, Franziska Schoenebeck, Debabrata Maiti
Article
Chemistry, Organic
Xingguo Jiang, Denise Meyer, Dominik Baran, Miguel A. Cortes Gonzalez, Kalman J. Szabo
JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Organic
Oriana Brea, Kalman J. Szabo, Fahmi Himo
JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Qiang Wang, Marvin Lubcke, Maria Biosca, Martin Hedberg, Lars Eriksson, Fahmi Himo, Kalman J. Szabo
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Chemistry, Multidisciplinary
Sybrand J. T. Jonker, Ramasamy Jayarajan, Tautvydas Kireilis, Marie Deliaval, Lars Eriksson, Kalman J. Szabo
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Chemistry, Multidisciplinary
Qiang Wang, Maria Biosca, Fahmi Himo, Kalman J. Szabo
Summary: The electrophilic fluorination of geminal alkyl substituted vinyl-Bmida derivatives proceeds via a bora-Wagner-Meerwein rearrangement, with the Bmida group having a larger migration aptitude than the alkyl moiety. This rearrangement occurs with a low activation barrier via a bora-cyclopropane shaped transition state according to DFT modelling studies.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Ramasamy Jayarajan, Tautvydas Kireilis, Lars Eriksson, Kalman J. Szabo
Summary: In this study, a variety of aliphatic, aromatic, and heterocyclic boronic acids were successfully modified using trifluorodiazoethane and BINOL derivatives, resulting in the synthesis of chiral trifluoromethyl containing boronic acid derivatives. The conversion of the chiral boronic acids to other compounds in situ was also demonstrated.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Qiang Wang, Lars Eriksson, Kalman J. Szabo
Summary: Homologation of trisubstituted fluoroalkenes followed by allylboration of aldehyde, ketone and imine substrates is a suitable method for the synthesis of beta-fluorohydrin and amine products. With the presence of (R)-iodo-BINOL catalyst, enantioselectivities up to 99% can be achieved by formation of a single stereoisomer with adjacent stereocenters, one of which is a tertiary C-F center.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Marie Deliaval, Ramasamy Jayarajan, Lars Eriksson, Kalman J. Szabo
Summary: We have developed a new three-component catalytic coupling reaction involving alkynyl boronates, diazomethanes, and aliphatic/aromatic ketones in the presence of BINOL derivatives. This reaction exhibits remarkably high enantio- and diastereoselectivity, leading to the formation of tertiary CF3-allenols with up to three contiguous stereocenters in a single step. The reaction proceeds under mild, neutral, and metal-free conditions, making it highly functional group tolerant.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Denise N. Meyer, Miguel A. Cortes Gonzalez, Xingguo Jiang, Linus Johansson-Holm, Monireh Pourghasemi Lati, Mathias Elgland, Patrik Nordeman, Gunnar Antoni, Kalman J. Szabo
Summary: A new method for fluorine-18 labelling of trifluoromethyl ketones has been developed, involving the conversion of an α-COCF3 functional group to a difluoro enol silyl ether followed by halogenation and fluorine-18 labelling. The utility of this method was demonstrated by synthesizing fluorine-18 labelled neutrophil elastase inhibitors, potentially useful for detecting inflammatory disorders.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Marvin Luebcke, Kalman J. Szabo
Summary: Diazocarbonyl compounds are utilized as substrates for di- and trifunctionalization reactions involving F/CF3/SCF3 introduction, with majority of reactions based on rhodium catalysis and involving oxygen nucleophiles. The oxyfluorination reactions have been further developed for new fluorine-18 labeling method, while an arylation-trifluoromethylthiolation reaction proceeds via a Hooz-type mechanism instead of rhodium catalysis.
Article
Chemistry, Multidisciplinary
Miguel A. Cortes Gonzalez, Xingguo Jiang, Patrik Nordeman, Gunnar Antoni, Kalman J. Szabo
CHEMICAL COMMUNICATIONS
(2019)
Article
Chemistry, Multidisciplinary
Marvin Lubcke, Dina Bezhan, Kalman J. Szabo
Article
Chemistry, Multidisciplinary
Sybrand J. T. Jonker, Colin Diner, Goeran Schulz, Hiroaki Iwamoto, Lars Eriksson, Kalman J. Szabo
CHEMICAL COMMUNICATIONS
(2018)
