Article
Chemistry, Multidisciplinary
Guanghao Huang, Regis Guillot, Cyrille Kouklovsky, Boris Maryasin, Aurelien de la Torre
Summary: A broadly applicable diastereo- and enantioselective inverse-electron-demand Diels-Alder reaction of 2-pyrones and acyclic enol ethers is reported, leading to the synthesis of bridged bicyclic lactones with high yields and enantioselectivities using a copper(II)-BOX catalytic system. Mechanistic studies suggest a stepwise mechanism, and the synthetic potential of the bridged bicyclic lactones is demonstrated through the enantioselective synthesis of polyfunctional cyclohexenes and cyclohexadienes, as well as a carbasugar unit.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Linghua Wang, Tao Li, Saima Perveen, Shuai Zhang, Xicheng Wang, Yizhao Ouyang, Pengfei Li
Summary: A nickel-catalyzed general, efficient, and highly enantioselective carboxylation reaction of racemic benzylic (pseudo)halides has been developed, utilizing atmospheric CO2 under mild conditions. A unique chiral 2,2'-bipyridine ligand enabled both high reactivity and stereoselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Shuai Zhang, Saima Perveen, Yizhao Ouyang, Liang Xu, Tao Yu, Min Zhao, Linghua Wang, Peidong Song, Pengfei Li
Summary: A new class of chiral bipyridine ligands, SBpy, featuring minimized steric hindrance and structural tunability, was designed and developed for the highly enantioselective Ni-catalyzed addition reaction. Compared to known methods, this reaction is more cost-effective and tolerant towards functional groups. The proposed reaction mechanism and stereocontrol model were based on experimental and computational results.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Saima Perveen, Shuai Zhang, Linghua Wang, Peidong Song, Yizhao Ouyang, Jiao Jiao, Xin-Hua Duan, Pengfei Li
Summary: The first nickel-catalyzed highly enantioselective reductive Ullmann coupling of ortho-chlorinated aryl aldehyde was achieved under mild reaction conditions using a chiral 2,2'-bipyridine ligand (+)-DTB-SBpy, resulting in the synthesis of axially chiral biphenyl or binaphthyl dials with high yields and enantioselectivities. The versatility of the products as common synthetic intermediates for diverse axially chiral ligands, catalysts, and functional molecules was demonstrated through short-step transformations. Additionally, this protocol enabled the concise and highly enantioselective formal total synthesis of biologically active natural products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Jiajing Li, Bing Yu, Zhan Lu
Summary: Imidazoline, as a structural analog of oxazoline, has gained significant attention in the rational design of chiral ligands due to its additional N-substituent allowing for fine-tuning of electronic and steric effects. Various chiral imidazoline ligands have been designed and employed in asymmetric organic reactions, expanding the applications of chiral synthesis.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Chen Li, Bin Chen, Xiaodong Ma, Xueling Mo, Guozhu Zhang
Summary: A catalytic asymmetric alkylation of azoles with secondary 1-arylalkyl bromides through direct C-H functionalization was reported. The reaction, under blue-light photoexcitation, showed good reactivity and high stereoselectivity, providing an efficient strategy for the construction of chiral alkyl azoles at low temperature. The reactions are compatible with a wide range of azoles.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
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
Ming Cui, Zhi-Yuan Zhao, Martin Oestreich
Summary: Chiral bis(phosphine) monooxides derived from C-2-symmetric bis(phosphines) have been found to exhibit superior enantioselection in copper-catalyzed conjugate borylation and 1,6-addition reactions. Specifically, (R,R)-Bozphos ligand shows significantly higher enantiomeric excesses and chemical yields compared to parent (R,R)-Me-Duphos ligand.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Qinglin Zhang, Kang Liang, Chang Guo
Summary: A novel electrolytic system has been introduced to divert standard ionic reactivity, providing a brand-new pattern of reactivity-electricity-driven asymmetric catalysis, which serves as a privileged chiral platform for enantioselective radical allylation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Peng Zhang, Qi Xu, Xiao-Mei Wang, Jia Feng, Chuan-Jun Lu, Yingzi Li, Ren-Rong Liu
Summary: The first enantioselective synthesis of N-N bisindole atropisomers via palladium-catalyzed construction of one indole skeleton is reported in this study. A wide variety of N-N axially chiral bisindoles were generated with good yields and excellent enantioselectivities through a cascade condensation/N-arylation reaction. The reaction mechanism and enantiocontrol were further investigated using density functional theory (DFT) calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Ken-Loon Choo, Bijan Mirabi, Karl Z. Demmans, Mark Lautens
Summary: Enantioenriched spiro-oxiranes with three contiguous stereocenters were synthesized using a rhodium-catalyzed cascade reaction, enabling the formation of a spirocyclic framework in a single step. Both sp(2)- and sp-hybridized carbon nucleophiles were found to be efficient initiators, yielding products with different functional groups. Derivatization studies demonstrated the synthetic versatility of the products' epoxide and alkyne moieties. DFT calculations were employed to explain spectroscopic discrepancies between solution- and solid-state structures of the products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Inorganic & Nuclear
Helene Pellissier
Summary: This review summarizes the recent developments in the use of TADDOL-derived phosphorus ligands in asymmetric metal catalysis, demonstrating their effectiveness in promoting various highly enantioselective transformations with different metals. (c) 2023 Elsevier B.V. All rights reserved.
COORDINATION CHEMISTRY REVIEWS
(2023)
Review
Chemistry, Multidisciplinary
Remi Jouhannet, Samuel Dagorne, Aurelien Blanc, Pierre de Fremont
Summary: This article summarizes the synthesis and applications of well-defined gold(III) complexes reported over the last fifteen years, exploring the applications of gold catalysis in organic chemistry and the potential of gold(III) complexes in pharmacology.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Mengyu Xue, Jinfeng Cui, Xiaotao Zhu, Fei Wang, Daqi Lv, Zaicheng Nie, Yajun Li, Hongli Bao
Summary: Chiral gamma-butyrolactones with two non-vicinal carbon stereocenters were efficiently synthesized using a well-designed copper/PyBox catalytic system. This method overcame the intrinsic stereoinduction of the close chirality center and achieved good to excellent enantioselectivities for both diastereoisomers. Additionally, the method selectively provided a single diastereoisomer through epimerization effect and synthesized all four diastereoisomers using opposite chiral ligands L2 and L2'. The obtained chiral gamma-butyrolactones can be further transformed into acyclic or cyclic molecules with two non-vicinal carbon stereocenters. Mechanistic studies revealed a linear relationship in this radical reaction, requiring less loading of ligand compared to the copper catalyst.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Raja K. K. Rit, Hongyi Li, Stephen P. P. Argent, Katherine M. M. Wheelhouse, Simon Woodward, Hon Wai Lam
Summary: Chiral dienes are important ligands in asymmetric catalysis but they are difficult to obtain. In this study, a simple chiral allenecarboxanilide was used to produce pseudoenantiomeric bicyclo[2.2.2]octa-2,5-dienes containing an alkenyl bromide via intramolecular [4+2] cycloaddition. These compounds can be easily functionalized to provide diverse chiral diene ligands. The synthesis is straightforward and can be conducted on a large scale. The resulting ligands exhibit high performance in nine types of enantioselective Rh(I)-catalyzed addition reactions.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Physical
Ivana Drienovska, Gerard Roelfes
Article
Chemistry, Physical
Zhi Zhou, Gerard Roelfes
Article
Chemistry, Physical
Cora Gutierrez de Souza, Gerard Roelfes, Manuela Bersellini
Article
Biochemistry & Molecular Biology
Ivana Drienovska, Remkes A. Scheele, Cora Gutierrez de Souza, Gerard Roelfes
Article
Chemistry, Multidisciplinary
Roos C. W. van Lier, A. Dowine de Bruijn, Gerard Roelfes
Summary: The study demonstrates a selective photocatalytic modification method for dehydroalanine residues in proteins and peptides, using a new water-soluble iridium(III) photoredox catalyst. This work suggests that photoredox catalysis using the newly designed catalyst is a promising strategy and could have great potential for novel bioconjugation strategies involving natural products containing dehydroalanine.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Reinder H. de Vries, Jakob H. Viel, Oscar P. Kuipers, Gerard Roelfes
Summary: This study describes the fast and selective chemical editing of ribosomally synthesized and post-translationally modified peptides (RiPPs) through beta-borylation of dehydroalanine residues. The method efficiently modifies various peptides, increasing their water solubility and maintaining antimicrobial activity. Additionally, the introduced boronic acid functionalities can be used for chemical mutagenesis and pH-controlled labeling of RiPPs.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Shreyans Chordia, Siddarth Narasimhan, Alessandra Lucini Paioni, Marc Baldus, Gerard Roelfes
Summary: The study demonstrates the supramolecular assembly of ArMs in E. coli cells and their application in enzyme catalysis. Improved mutants were obtained through directed evolution, and the whole-cell ArM system showed catalytic activity without the need for engineering.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Ruben V. Maaskant, Shreyans Chordia, Gerard Roelfes
Summary: The research focused on combining transition-metal catalysis with whole-cell biocatalysis to derivatize styrene. Using ruthenium and palladium catalysts, different product derivatives could be obtained from the whole-cell biosynthesis of styrene.
Article
Biochemistry & Molecular Biology
Aditya Iyer, Maxim Baranov, Alexander J. Foster, Shreyans Chordia, Gerard Roelfes, Rifka Vlijm, Geert van den Bogaart, Bert Poolman
Summary: The study developed noncovalent fluorogenic protein tags in bacteria using transcription factor-based tags, CTPEs, to enable long-term fluorescence microscopy of living bacterial cells. This provides a general tool for investigating cellular protein localization and dynamics, protein-protein interactions, and prolonged live-cell microscopy, even under oxygen-free conditions.
ACS CHEMICAL BIOLOGY
(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, Physical
Zhi Zhou, Gerard Roelfes
Summary: The article describes a tandem Michael addition/enantioselective protonation reaction catalyzed by an artificial enzyme in water. Through the use of abiological catalytic sites and a Lewis acid Cu(II) complex, high stereocontrol was achieved. This illustrates the potential of exploiting synergistic catalysis in artificial enzymes for challenging reactions.
Article
Chemistry, Physical
Reuben B. Leveson-Gower, Zhi Zhou, Ivana Drienovska, Gerard Roelfes
Summary: Incorporating noncanonical amino acid para-aminophenylalanine into a nonenzymatic protein scaffold creates a proficient and stereoselective artificial enzyme for specific reactions. Analysis of evolved mutants reveals different catalytic activities and reaction pathways.
Article
Chemistry, Physical
Reuben B. Leveson-Gower, Ruben M. de Boer, Gerard Roelfes
Summary: The incorporation of organocatalysts into protein scaffolds offers a solution for overcoming limitations in catalysis. This study demonstrates the successful incorporation of para-aminophenylalanine into a non-enzymatic protein scaffold, resulting in a proficient and enantioselective artificial enzyme for the Friedel-Crafts alkylation reaction.
Review
Chemistry, Physical
Reuben B. Leveson-Gower, Gerard Roelfes
Summary: Friedel-Crafts alkylation and acylation reactions are important in synthetic and industrial chemistry. Researchers have expanded the application of these reactions through directed evolution and created bio-hybrid catalysts. This review summarizes these efforts and discusses future routes for more efficient and benign Friedel-Crafts reactions.
Article
Chemistry, Multidisciplinary
Linda Ofori Atta, Zhi Zhou, Gerard Roelfes
Summary: This study reports an artificial-enzyme-catalysed biocatalytic cascade that promotes reactions that have no equivalent in nature. By conducting in vivo biocatalytic cascades inside E. coli cells, this research takes an important step towards achieving a hybrid metabolism.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)