Article
Chemistry, Organic
Yuerong Wang, Pengfei Jia, Yingdi Hao, Jianglian Li, Ruizhi Lai, Li Guo, Yong Wu
Summary: In this study, metal-free blue light-mediated [2,3]-sigmatropic rearrangement reactions of tosylhydrazones and sulfides were reported. This strategy showed significant improvement compared to traditional methods due to stable starting materials and mild reaction conditions. The Doyle-Kirmse reaction and Sommelet-Hauser reaction were developed with simple operation, high yields, and broad substrate adaptability.
TETRAHEDRON LETTERS
(2022)
Article
Chemistry, Organic
Mariliis Kimm, Ivar Jarving, Maksim Oseka, Tonis Kanger
Summary: Asymmetric rearrangement reactions are highlighted as a perfect tool for constructing new carbon-carbon bonds in an enantioselective manner. The article specifically discusses a new and straightforward procedure for synthesizing alpha-hydroxy ketones with high diastereo- and enantioselectivity through the enantioselective [2,3]-Wittig rearrangement of cinnamyloxycyclohexanone derivatives catalyzed by a commercially available primary amine.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Guanqun Zhang, Abdullah S. Alshreimi, Laura Alonso, Alan Antar, Hsien-Cheng Yu, Shahidul M. Islam, Laura L. Anderson
Summary: A new method for the synthesis of 1-pyrrolines with high regio- and diastereoselectivity has been explored using N-alkenylnitrones and alkynes, with mechanistic studies providing insight into the balance of steric and electronic effects that control the product preferences. This cascade reaction demonstrates the divergent synthetic utility of the new method through diastereoselective derivatization of the 1-pyrrolines prepared.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Biochemistry & Molecular Biology
Gerard Roelfes
Summary: Heme enzymes are versatile catalysts in nature and can catalyze reactions where there are no equivalents in nature. Approaches to create enzymes for cyclopropanation include repurposing of heme enzymes, strategies to improve these enzymes, and artificial heme enzymes. Lessons learned from mechanism and design principles are discussed in this review.
JOURNAL OF INORGANIC BIOCHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Adam B. Riddell, Michelle M. Michalski, Monika R. Snowdon, Mark J. Hirst, Adrian L. Schwan
Summary: Sulfenyl chlorides can be used to access allenyl sulfoxides through sulfenate ester formation and [2,3]-sigmatropic rearrangement reactions. Thiosuccinimides are shown to be a viable alternative to sulfenyl chlorides for the synthesis of a variety of compounds.
Review
Chemistry, Organic
Claire Empel, Sripati Jana, Rene M. Koenigs
Summary: This review article summarizes the progress made on [1,2]-sigmatropic rearrangements using carbenes in the ylide formation step, highlighting the application of diazoalkanes as carbene precursors and the formation and application of various ylide species.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Physical
Haitao Liu, Feng Chen, Nannan Zhao, Sai V. C. Vummaleti, Michael B. Sullivan, Jackie Y. Ying, Lei Wang
Summary: Ring expansion reactions are efficient tools in synthetic and medicinal chemistry, but the strategy involving sulfur ylide-initiated [1,4]-sigmatropic rearrangement is still underexploited. In this study, a rhodium-catalyzed ring expansion of thiochromenes and aromatic thiophenes was disclosed, enabling the straightforward assembly of polyaromatic oxathionines and oxathiocines with diverse functionalities.
Article
Chemistry, Physical
Haitao Liu, Feng Chen, Nannan Zhao, Sai V. C. Vummaleti, Michael B. Sullivan, Jackie Y. Ying, Lei Wang
Summary: A rhodium-catalyzed ring expansion reaction has been discovered for the synthesis of polyaromatic oxathionines and oxathiocines with diverse functionalities.
Article
Chemistry, Organic
Michael Shevlin, Neil A. Strotman, Laura L. Anderson
Summary: A concise new synthetic route to furo[2,3-b]indolines has been developed by utilizing the reactivity of N-alkenyloxyindole intermediates. These compounds undergo spontaneous [3,3]-sigmatropic rearrangement followed by cyclization to form hemiaminals as single diastereomers. The tin-promoted formation of N-hydroxyindole followed by conjugate addition to activated alkynes provides simple and modular access to a diverse array of N-alkenyloxyindoles and their corresponding furo[2,3-b]indolines.
Review
Chemistry, Multidisciplinary
Andres Felipe Leon Rojas, Sara Helen Kyne, Philip Wai Hong Chan
Summary: Late-transition-metal-based complexes are essential catalysts in chemical synthesis, as they can rapidly and efficiently increase molecular complexity from readily accessible substrates. The control over product selectivities achieved by these catalysts, in terms of chemoselectivity, diastereoselectivity, enantioselectivity, and site-selectivity, is remarkable and has enabled a wide range of functional group transformations.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Inorganic & Nuclear
Adam B. Riddell, Michelle M. Michalski, Adrian L. Schwan
Summary: By exploring alternative sources of electrophilic sulfur, thiosuccinimides were found to be a viable sulfur source for the synthesis of alkyl allenyl sulfoxides via the [2,3]-sigmatropic rearrangement. With optimized conditions, a variety of alkyl allenyl sulfoxides were synthesized in fair to good yields. Additionally, butyn-1,4-diols can be selectively monofunctionalized to form 1-hydroxyalkyl allenyl sulfoxides or bis-functionalized to form 2,3-disubstitued dienes.
PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS
(2023)
Article
Chemistry, Organic
Keisuke Iwata, Yasunobu Egawa, Katsunori Yamanishi, Hayato Tsuji
Summary: The acid-induced intramolecular cyclization of 1,1-disubstituted 3-aryl-2,3-dibromoallylalcohols leads to the formation of 2,3-dibromo-1H-indene derivatives and tetrabromodihydro-s-indacenes. These multi-brominated compounds can serve as versatile building blocks for the synthesis of various indene and indacene derivatives. The synthesis of dialkylmethylene-bridged oligo(phenylenevinylene)s demonstrates the attractive photophysical properties of these compounds.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Zhe-Ran Chang, Si-Si Du, Cui Zhang, Shuang-Hu Chen, Yuan-Zhao Hua, Min-Can Wang, Guang-Jian Mei, Shi-Kun Jia
Summary: An efficient kinetic resolution of racemic trans-2,3-aziridinyl alcohols is achieved through zinc catalyzed ring opening reactions with different amines as nucleophiles. The directing effect of the hydroxyl group and the precise enantiodiscrimination by a dinuclear zinc cooperative catalyst are crucial for high regioselectivity and enantioselectivity. Various enantioenriched vicinal diamines and trans-2,3-aziridinyl alcohols are obtained in good yields with excellent ee values. This study represents the first example of directed enantioselective nucleophilic ring opening reactions of 2,3-aziridinyl alcohols.
Article
Chemistry, Applied
Maxim R. Demidov, Dmitry Osipov, Konstantin A. Korol'kov, Vitaly A. Osyanin
Summary: A variety of trans-2-acyl-2,3-dihydrofurans have been assembled and rearranged into annulated 4H-pyrans using Sm/TMSCl or Zn/ZrCl4 redox systems. The rearrangement involves SET reduction of carbonyl group to carbene followed by rare [1,2]-aroxyl shift. The use of Zn/ZrCl4 redox system enriched the synthetic toolbar.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Review
Multidisciplinary Sciences
Michal Rachwalski, Aleksandra Buchcic-Szychowska, Stanislaw Lesniak
Summary: This review article presents the achievements of selected asymmetric synthesis reactions in the last three years, focusing on asymmetric cyclopropanation, Friedel-Crafts reaction, Mannich and Michael reaction, and other stereoselective processes catalyzed by chiral systems. These transformations rely on the use of appropriate chiral catalysts to control both the chemical and stereochemical outcomes, leading to optically pure or enantiomerically enriched products with potential applications in various fields.
Article
Chemistry, Multidisciplinary
Keihann Yavari, Wylliam Delaunay, Nicolas De Rycke, Thibault Reynaldo, Paul Aillard, Monika Srebro-Hooper, Victoria Y. Chang, Gilles Muller, Denis Tondelier, Bernard Geffroy, Arnaud Voituriez, Angela Marinetti, Muriel Hissler, Jeanne Crassous
CHEMISTRY-A EUROPEAN JOURNAL
(2019)
Article
Chemistry, Organic
Rajendra K. Mallick, Shubham Dutta, Rajeshwer Vanjari, Arnaud Voituriez, Akhila K. Sahoo
JOURNAL OF ORGANIC CHEMISTRY
(2019)
Article
Chemistry, Multidisciplinary
Julie Febvay, Charles S. Demmer, Pascal Retailleau, Jeanne Crassous, Laura Abella, Jochen Autschbach, Arnaud Voituriez, Angela Marinetti
CHEMISTRY-A EUROPEAN JOURNAL
(2019)
Article
Chemistry, Multidisciplinary
Zhenhao Zhang, Vitalii Smal, Pascal Retailleau, Arnaud Voituriez, Gilles Frison, Angela Marinetti, Xavier Guinchard
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Article
Chemistry, Physical
Valentin Magne, Youssouf Sanogo, Charles S. Demmer, Pascal Retailleau, Angela Marinetti, Xavier Guinchard, Arnaud Voituriez
Review
Chemistry, Physical
Fabrizio Medici, Nawel Goual, Vincent Delattre, Arnaud Voituriez, Angela Marinetti
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.
Article
Chemistry, Organic
Charlotte Lorton, Nidal Saleh, Arnaud Voituriez
Summary: Phosphine-catalyzed tandem Michael addition/intramolecular Wittig reactions have been developed for the synthesis of chiral compounds. Catalytic and asymmetric P(III)/P(V) processes were implemented using enantiopure chiral phosphines.
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, 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)
Article
Chemistry, Multidisciplinary
Xu Han, Pascal Retailleau, Vincent Gandon, Arnaud Voituriez
CHEMICAL COMMUNICATIONS
(2020)
