Article
Chemistry, Multidisciplinary
Chenxiao Qian, Pengfei Li, Jianwei Sun
Summary: A catalytic enantioselective variant of oxidative rearrangement of indoles to access oxindoles has been developed using chiral phosphoric acid catalysis, providing a rapid access to a range of enantioenriched spirooxindoles with high enantioselectivity controlled by dynamic kinetic resolution.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Rui-Han Dai, Qi Wang, Zhi-Xiong Chen, Shi-Kai Tian
Summary: An unprecedented asymmetric aza-Claisen rearrangement was discovered to proceed without catalysts and additives, providing easy access to structurally diverse delta-chiral beta-diketones with high yields and excellent retention of enantiopurity. This protocol proved powerful for the construction of an all-carbon quaternary stereocenter with high enantiopurity.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Lifeng Wang, Yuqiao Zhou, Zhishan Su, Fengcai Zhang, Weidi Cao, Xiaohua Liu, Xiaoming Feng
Summary: This study discovered the thermal para-Claisen rearrangement of naphthyl 1-propargyl ethers and elucidated its mechanism for constructing stereogenic centers. By controlling the reaction conditions and catalyst selection, organic molecules with different substitutions can be efficiently synthesized.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Huijin Lee, Ki Tae Kim, Min Kim, Cheoljae Kim
Summary: This review presents the recent advancements in catalytic [3,3]-sigmatropic rearrangements since 2016. By introducing catalytic systems, highly functionalized substrates can be formed under mild conditions and asymmetric synthesis can be achieved using chiral catalytic systems. Detailed reaction mechanisms are discussed to understand the reactivity and selectivity of the reactions. Finally, this review inspires the development of new cascade reaction pathways utilizing catalytic [3,3]-sigmatropic rearrangement as related methodologies for the synthesis of complex functional molecules.
Article
Chemistry, Organic
Ping Wei, Yiwen Zhu, Jun Ying, Xiao-Feng Wu
Summary: Cobalt(II) salt has been widely used as a non-noble metal catalyst for direct C-H bond functionalization. In this study, we developed a cobalt-catalyzed reaction for the rapid construction of 2-alkoxylindole scaffolds from the C-H cleavage and alkoxylation of indoles with alcohols. The reaction proceeded well with Co(acac)2 as the catalyst, yielding a variety of 2-alkoxylindole derivatives in moderate to high yields. Control experiments suggested a radical process involving Co(III) species as the active catalyst.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Joshua A. Malone, Satish Chandra Philkhana, Jacob R. Stepherson, Fatimat O. Badmus, Frank R. Fronczek, Rendy Kartika
Summary: This article describes a new synthetic reaction that can generate all-carbon bisquaternary centers at the opposing side of alpha-carbons in cyclohexanone with four different substituents in a controlled manner.
Article
Chemistry, Physical
Lei Xu, Sishi Zhong, Qian Yang, Jie Wei, Jiaming Zou, Hongxiang Li, Yunfei Cai
Summary: This study developed a new asymmetric radical-mediated Piancatelli-type rearrangement reaction, which allows for a three-component reaction of diverse carbon-centered radical precursors and anilines with high yields, enantioselectivities, and diastereoselectivities. The synthesized products can be applied for late-stage functionalization of valuable drug targets or natural products. The diastereoselectivity of the rearrangement reaction is controlled by Dy(III)-accelerated Z/E isomerization of Piancatelli intermediates, and the chiral Bronsted acid-catalyzed 4π-electrocyclization of pentadienyl carbocation intermediates is a key step determining both reaction rate and enantioselectivity.
Article
Multidisciplinary Sciences
Can Yang, Xiaoyu Zhou, Lixing Shen, Zhuofeng Ke, Huanfeng Jiang, Wei Zeng
Summary: The authors developed a Mn(I)-catalyzed sigmatropic rearrangement of beta, gamma-unsaturated alcohols via C-C sigma bond activation. This rearrangement allows for selective reorganization of carbon skeletons, providing a strategy for the synthesis of complex structures with high atom and step economy.
NATURE COMMUNICATIONS
(2023)
Review
Chemistry, Inorganic & Nuclear
Chong-Yang Shi, Long Li, Wei Kang, Yan-Xin Zheng, Long-Wu Ye
Summary: The efficient and selective construction of carbon-carbon bond in an atom-economic and mild way remains a core aspect of modern organic synthesis. The strategy of Claisen rearrangement triggered by catalytic alkyne alkoxylation has unique advantages and has attracted widespread attention in the past two decades. Both intramolecular and intermolecular protocols provide practical and facile approaches for the synthesis of complex compounds with valuable core skeletons.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Applied
Camille Van Wesemael, Nicolas Brach, Mihaela Gulea, Gaelle Blond
Summary: A series of 3-allenyl benzo[b]thiophenes were synthesized through a gold(I)-catalyzed domino reaction. The process involves a 5-endo-dig cyclization with C S bond formation and consecutive S-to-C propargyl migration via [3,3]-sigmatropic Claisen rearrangement. Various fused O-heterocycles can be obtained from a substrate bearing a 3-butynol moiety via intramolecular hydroalkoxylation. The gold-mediated 1,3-migration involving allenyl to propargyl rearrangement is also described.
ADVANCED SYNTHESIS & CATALYSIS
(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
Gorka Garay, Josebe Hurtado, Manuel Pedron, Lorena Garcia, Efraim Reyes, Eduardo Sanchez-Diez, Tomas Tejero, Luisa Carrillo, Pedro Merino, Jose L. Vicario
Summary: We have demonstrated the catalytic and enantioselective rearrangement of vinylcyclopropane-cyclopentene, using (vinylcyclopropyl)acetaldehydes as starting materials and enamine intermediates for activation. The reaction involves the generation of a donor-acceptor cyclopropane, leading to the formation of an acyclic iminium ion/dienolate intermediate where stereochemistry is erased. The final cyclization step results in the stereocontrolled formation of various structurally distinct cyclopentenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jing Liu, Yusheng Yang, Weiming Shi, Zhi-Xiang Yu
Summary: We present computational evidence for a metalla-Claisen rearrangement (MCR) in the gold-catalyzed [4+2] cycloaddition reaction of yne-dienes. The reaction proceeds through exo cyclopropanation, followed by MCR and reductive elimination. The presence of a cyclopropane moiety formed in the initial step greatly facilitates the MCR process. Additionally, we explore the significance of the combination of tether group and terminal substituent on alkyne in the yne-diene substrates. We also investigate whether an MCR mechanism is involved in the rhodium-catalyzed [4+2] reaction of yne-dienes. These findings and insights represent a significant advancement in the field of catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Applied
Sara Meninno, Francesca Franco, Maurizio Benaglia, Alessandra Lattanzi
Summary: Pyrazoleamides have gained attention as reactive and practical surrogates in asymmetric catalysis, particularly in a variety of metal- and organocatalytic transformations. Their relevance has extended to photoredox catalysis and challenging stereoselective bond-forming reactions in recent years.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Vibha V. Kanale, Christopher Uyeda
Summary: Cobalt catalysts facilitate highly enantioselective ring-opening reactions of 2,5-dihydrofurans using vinylidenes. The resulting products are acyclic organozinc compounds, capable of further functionalization with an electrophile. The proposed mechanism involves the formation of a cobalt vinylidene species that adds to the alkene via a [2+2]-cycloaddition pathway, followed by ring-opening through outer-sphere & beta;-O elimination assisted by a ZnX2 Lewis acid. DFT models explain the observed stereochemical outcome by suppressing competing inner-sphere syn & beta;-H and & beta;-O elimination pathways due to the geometric constraints of the metallacycle intermediate. Cobalt catalysts also promote enantioselective ring-opening reactions of unstrained heterocycles via reductive addition of 1,1-dichloroalkenes. The resulting products are acyclic homoallylic alcohols with a vinylzinc motif, which can be further modified with an electrophile. Mechanistic studies suggest that the ring-opening occurs through outer-sphere & beta;-O elimination facilitated by a Zn(II) Lewis acid.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Alexander Reichle, Hannes Sterzel, Peter Kreitmeier, Remi Fayad, Felix N. Castellano, Julia Rehbein, Oliver Reiser
Summary: The study showcases the concept of light-induced homolysis for radical generation in Cu-II-photocatalyzed decarboxylative oxygenation. Two Cu-II-carboxylate complexes with different coordination geometries were synthesized and characterized by X-ray analysis, correlating their structure with their ability to initiate light-induced decarboxylations.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Quan-Qing Zhao, Julia Rehbein, Oliver Reiser
Summary: This study presents a visible-light-driven dearomatization reaction of unactivated arenes, enabling efficient synthesis of spiro-1,4-cyclohexadienes. Calculations indicate that the overall process is thermoneutral, highlighting the potential of light-driven processes in developing sustainable transformations that defy thermodynamic requirements.
Review
Chemistry, Medicinal
Gloria Betzenbichler, Laura Huber, Sabrina Kraeh, Marie-Louise K. Morkos, Alexander F. Siegle, Oliver Trapp
Summary: Chiral compounds are crucial in biochemical processes, chiroptical materials, and pharmaceuticals. The analysis and separation of chiral compounds are of great significance in scientific, industrial, and economic fields. Chiral gas chromatography and high-performance liquid chromatography have played a vital role in asymmetric synthesis and catalysis in diverse fields of chemistry.
Article
Chemistry, Medicinal
Stefanie Auras, Oliver Trapp
Summary: Chiral compounds with a 1,2-diamine structure motif and their derivatives are widely studied and have various applications in organic chemistry, particularly in asymmetric transformations. In this study, a simple and diastereoselective synthesis for a diamide-bridged biaryl ligand is presented. The resulting ligand showed high diastereomeric and enantiomeric purity, as confirmed by NMR spectroscopy and DFT calculations. This research is significant for the utilization and further development of chiral compounds.
Article
Biology
Klaus Paschek, Kai Kohler, Ben K. D. Pearce, Kevin Lange, Thomas K. Henning, Oliver Trapp, Ralph E. Pudritz, Dmitry A. Semenov
Summary: The origin of life on early Earth might be closely related to the formation of ribose in carbonaceous chondrites, which is a crucial component of the RNA world. Through laboratory experiments and theoretical calculations, researchers found that the aqueous formose reaction could produce a significant amount of ribose in carbonaceous chondrites. This discovery sheds light on the possible synthesis of life-building blocks on Earth.
Article
Chemistry, Physical
Sabrina Kraeh, Iris Kachel, Oliver Trapp
Summary: Palladium-catalyzed cross-coupling reactions are efficient methods for organic synthesis, but heteroatom-containing compounds often complicate these reactions. This study introduces a highly active phosphine ligand that enables excellent yields in C-N coupling reactions at ambient temperature. The unique structure of the ligand, incorporating a silicon atom and a cyclohexane moiety, results in electron-rich properties. This ligand facilitates a broad range of coupling reactions under mild conditions in palladium catalysis.
Article
Chemistry, Organic
Jan-Michael Menke, Oliver Trapp
Summary: For the preparation of chiral drugs, the combination of stereochemically stable and flexible catalysts with chiral auxiliaries is crucial. In this study, a successful approach to the spontaneous deracemization of tropos ligands for asymmetric catalysis was demonstrated.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Editorial Material
Biochemistry & Molecular Biology
Oliver Trapp
Article
Biology
Laura Huber, Oliver Trapp
Summary: This study developed a method to investigate the reaction kinetics of single molecules in order to understand chiral symmetry breaking at the molecular level. The results showed that interlocking processes can amplify the occurrence of symmetry breaking, providing a promising direction for experimental implementation and identification of these processes.
ORIGINS OF LIFE AND EVOLUTION OF BIOSPHERES
(2022)
Article
Multidisciplinary Sciences
Guiyang Yao, Simone Kosol, Marius T. Wenz, Elisabeth Irran, Bettina G. Keller, Oliver Trapp, Roderich D. Suessmuth
Summary: This article reports the use of the term "ansamer" to describe the isomers of the bicyclic octapeptide alpha-Amanitin. The researchers synthesized analogs of alpha-Amanitin and analyzed their isomers, proposing and describing the term "ansamer" for these isomers.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Constanze Sydow, Christiane Seiband, Alexander F. Siegle, Oliver Trapp
Summary: Organophosphates play important roles in living organisms, but their prebiotic origins are unknown. In this study, the authors demonstrate the efficient formation of organophosphates through a phosphorylation reaction in liquid sulfur dioxide at room temperature. This reaction could have occurred in volcanic environments on Early Earth, and it also has potential applications in synthetic chemistry.
COMMUNICATIONS CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Lena C. Mayer, Simone Heitsch, Oliver Trapp
Summary: Asymmetric synthesis plays a crucial role in preparing enantiomerically pure compounds and controlling individual stereocenters in complex compound synthesis. It relies on the use of enantiopure catalysts and configurationally flexible ligands or organocatalysts. The design of smart catalyst systems that combine supramolecular recognition, stereoconvergent alignment, and catalysis has been successful in enhancing enantioselectivity in asymmetric catalysis.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Medicinal
Simone Heitsch, Lena Carina Mayer, Yanis Luca Pignot, Oliver Trapp
Summary: Soai's asymmetric autocatalysis is a remarkable example of symmetry breaking and enantioselective amplification in the alkylation of pyrimidine-5-carbaldehydes. Zinc hemiacetalate complexes formed from the aldehydes and the chiral product alcohol were identified as highly active catalysts in this transformation. By studying the synthesis of coumarin homolog biaryl systems, it was found that they can form hemiacetals through intramolecular cyclization, with the ability to enable or disable this process depending on the tropos or atropos configuration.
Article
Chemistry, Multidisciplinary
Constanze Sydow, Fabian Sauer, Alexander F. Siegle, Oliver Trapp
Summary: Peptides play essential roles in the structure and catalytic functions of living organisms. The formation of peptides faces thermodynamic and kinetic barriers. Recent studies have explored various formation scenarios during the origin of life, including iron(III)-catalyzed condensations. However, iron(III)-catalysts often have low catalytic activity at elevated temperatures. This study demonstrates that reduced iron activated by acetic acid efficiently mediates peptide formation, providing a potential pathway for the formation of the first peptides in anoxic environments.
Review
Chemistry, Multidisciplinary
Lena C. Mayer, Simone Heitsch, Oliver Trapp
Summary: Asymmetric synthesis is a crucial technique for the preparation of chiral compounds and the control of stereocenters in complex syntheses. Configurationally flexible ligands and catalysts can be enriched through dynamic processes, leading to improved enantioselectivity in asymmetric catalysis. This strategy has significant implications for the development of new catalytic applications and understanding of chirality amplification and homochirality in biological systems.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
