Article
Chemistry, Multidisciplinary
Julian Baars, Isabelle Grimm, Dirk Blunk, Joerg-Martin Neudoerfl, Hans-Guenther Schmalz
Summary: A 12-step total synthesis of the natural product dysiherbol A was achieved, revealing the need for revision of the originally proposed structure and absolute configuration. The synthesis involved key steps including Cu-catalyzed addition/enolate-trapping, Au-catalyzed double cyclization, and late installation of the C5-bridgehead methyl group. Spectroscopic measurements confirmed the identity of the synthetic compound with the natural product but with an opposite molecular rotation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Marina Briand, Elsa Anselmi, Guillaume Dagousset, Emmanuel Magnier
Summary: In recent years, the number of methods for synthesizing asymmetric molecules with a perfluoroalkylated chain has been limited, with only a few applicable to a wide variety of scaffolds. This microreview summarizes the recent advances in enantioselective perfluoroalkylation (-CF3, -CF2H, -CnF2n+1) and emphasizes the need for new enantioselective methods to easily synthesize chiral fluorinated molecules that would be useful for the pharmaceutical and agrochemical industries. Some perspectives are also mentioned.
Review
Chemistry, Multidisciplinary
Martin Aleksiev, OlgaGarcia Mancheno
Summary: Catalytic asymmetric dearomatization of heteroaromatic compounds has attracted significant attention as it enables the rapid expansion of chemical space by converting simple, flat molecules into complex, three-dimensional structures with added value. Among different approaches, organocatalytic dearomatization methods, especially anion-binding catalysis technology, have shown remarkable progress, providing new means for enantioselective dearomatization of heteroarenes through chiral contact ion pair formation by activating the electrophilic reaction partner. This article provides an overview of different methodologies and advances in anion-binding catalyzed dearomatization reactions of heteroarenes.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Ying-Pong Lam, Jingxian Huang, Xiaojian Jiang, Ying-Yeung Yeung
Summary: A class of cinchona alkaloid-derived zwitterions has been successfully used to achieve highly enantioselective Steglich rearrangement and the same catalytic protocol was found applicable in the asymmetric aldol reaction. Studies were conducted to elucidate a clearer mechanism.
Article
Chemistry, Multidisciplinary
Harvey J. A. Dale, George R. Hodges, Guy C. Lloyd-Jones
Summary: By conducting a series of experiments and calculations, the azole-catalyzed aminolysis of p-fluorophenyl acetate and its mechanism were investigated. It was found that changes in solvent, auxiliary base, and azole catalyst could significantly affect the reaction kinetics. The study revealed a diverse range of kinetics and emphasized the importance of considering catalyst speciation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Organic
Yulong Zhang, Yushuang Chen
Summary: This review presents recent breakthroughs in catalytic asymmetric [1,3]-rearrangement processes over the past decade, including transition metal catalysis, nucleophilic catalysis, Bronsted acid catalysis, and Lewis acid catalysis. The article also discusses most of the reaction mechanisms, providing insights for readers to comprehensively and systematically understand this exciting research field.
ORGANIC CHEMISTRY FRONTIERS
(2022)
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)
Review
Chemistry, Multidisciplinary
Dian-Feng Chen, Liu-Zhu Gong
Summary: This article introduces the fundamental attributes of asymmetric organo/transition-metal combined catalysis (AOMC), explains how organocatalysts and transition-metal complexes collaborate, and discusses future opportunities in this field.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Review
Chemistry, Multidisciplinary
Johannes Grosskopf, Thorsten Bach
Summary: Upon irradiation with a suitable chiral catalyst, racemic compounds can be converted into enantiopure compounds through a process called photochemical deracemization. This review comprehensively covers the research and current developments in this field, discussing the reactions and mechanistic details underlying the presented reaction. Photochemical deracemization offers a unique opportunity to directly obtain enantiopure compounds from racemates, and short-lived intermediates play a key role in determining the enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Na Shao, Xueyang Liu, Valerie Monnier, Laurence Charles, Jean Rodriguez, Cyril Bressy, Adrien Quintard
Summary: This research presents a simple strategy for the elaboration of enantioenriched complex acyclic stereotriads through a sequence of two unprecedented steps. By combining a diastereoselective aldol-Tishchenko reaction and an enantioselective organocatalyzed kinetic resolution, compounds with fluorinated tetrasubstituted stereocenters can be efficiently synthesized with excellent selectivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Na Shao, Xueyang Liu, Valerie Monnier, Laurence Charles, Jean Rodriguez, Cyril Bressy, Adrien Quintard
Summary: The authors developed a simple strategy to synthesize enantioenriched complex acyclic stereotriads with fluorinated tetrasubstituted stereocenters, by combining a diastereoselective aldol-Tishchenko reaction and an enantioselective organocatalyzed kinetic resolution in two unprecedented steps. The aldol-Tishchenko reaction directly generated a large panel of acyclic 1,3-diols possessing a fluorinated tetrasubstituted stereocenter with excellent diastereocontrol, while the subsequent organocatalyzed kinetic resolution produced the desired enantioenriched stereotriads with high selectivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Review
Chemistry, Inorganic & Nuclear
Heng Liu, Sayantani Saha, Moris S. Eisen
Summary: Hydroamination is an atom-economic reaction that efficiently constructs C-N bonds by adding an NH unit into CC/CX multiple bonds. The development of organo- lanthanides and actinides mediated hydroamination can be divided into three stages, with the third stage focusing on post-transition metal complexes.
COORDINATION CHEMISTRY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Jianfeng Jiang, Xia Wang, Shengping Liu, Sichen Zhang, Binmiao Yang, Yu Zhao, Shenci Lu
Summary: We report an unprecedented gold and oxidative NHC relay catalysis for highly enantioselective cascade annulation between readily available alpha-amino-ynones with enals. This method utilizes in situ-generated pyrrolin-4-ones as a novel and versatile synthon, reacting with alpha,beta-unsaturated acylazolium intermediates generated from enals by oxidative NHC catalysis to produce pyrrole-fused lactones in high yield and excellent enantioselectivity. The utility of the lactone products is demonstrated by their facile conversion to densely functionalized pyrroles and pyrrolin-4-ones with high yields and excellent stereopurity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Chaoqi Ke, Zhenzhong Liu, Sai Ruan, Xiaoming Feng, Xiaohua Liu
Summary: An easily available L-proline-derived guanidine-amide was found to efficiently catalyze the [4 + 2] cycloaddition of azlactones with 2-benzothiazolimines, yielding various benzothiazolopyrimidines with adjacent tertiary and quaternary stereogenic centers in excellent yields at a loading of 2 mol%. The diastereoisomers of the main adducts were different from those in a previous bifunctional organocatalytic system.
ORGANIC CHEMISTRY FRONTIERS
(2021)