Article
Chemistry, Organic
Takashi Mino, Kaho Takaya, Kaito Koki, Natsume Akimoto, Yasushi Yoshida, Yoshio Kasashima, Masami Sakamoto
Summary: We synthesized N-alkyl-N-cinnamoyl amide type phosphine-olefin compounds 1 and observed axial chirality in the C(aryl)-N(amide) bond of compounds 1 using HPLC analysis with a chiral stationary phase column. Enantiomeric isomers of 1 were obtained and (-)-1 was demonstrated as a chiral ligand in Pd-catalyzed asymmetric allylic substitution reactions, leading to high enantioselectivity (up to 97% ee) in the esterification process.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jeanne Masson-Makdissi, Liher Prieto, Xavier Abel-Snape, Mark Lautens
Summary: This study demonstrates the feasibility and advantages of combining two distinct asymmetric transition-metal-catalyzed reactions in one pot, effectively converting simple allyl enol carbonate precursors into enantioenriched cyclic ketones. Despite the challenges in controlling stereoselectivity, the products are obtained with high enantiomeric excesses exceeding 99% ee, surpassing those obtained from individual reactions. Additionally, the one-pot reaction is enantio- and diastereodivergent, allowing easy access to all stereoisomers from the same starting materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Takashi Mino, Yohei Fujisawa, Shizuki Yoshida, Mitsuru Hirama, Takumu Akiyama, Ryo Saito, Yasushi Yoshida, Yoshio Kasashima, Masami Sakamoto
Summary: By synthesizing cinnamoyl amide type chiral P,olefin ligand (S)-4, separable diastereomers of 4d were obtained successfully, and asymmetric allylic substitution reactions of indoles using (S,aS)-4d as a chiral ligand demonstrated high enantioselectivities (up to 98% ee).
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Physical
Li-Xia Liu, Wen-Jun Huang, Qing-Xian Xie, Bo Wu, Chang-Bin Yu, Yong-Gui Zhou
Summary: The research proposed a new strategy for dynamic kinetic resolution, successfully achieving enantioselective separation of flavonoid compounds and forming two stereogenic centers, providing a new way for organic synthesis.
Article
Chemistry, Physical
Jeanne Masson-Makdissi, Justin Ching, Cian M. Reid, Mark Lautens
Summary: A dual metal approach enables the use of unsymmetrical diallyl carbonates as viable enolate precursors for allylic alkylation reactions, allowing facile access to various alpha-quaternary allylated aldehydes and ketones. This methodology involves regioselective Pd-catalyzed decarboxylative oxidative addition and Rh-catalyzed isomerization.
Article
Chemistry, Physical
Wen-Qian Zhang, Hong-Cheng Shen
Summary: All-carbon quaternary stereocenters are important components of natural products and bioactive compounds, and a nickel and chiral amine cooperative catalysis has been disclosed to enable highly enantioselective allylic alkylation reactions. This method allows for the synthesis of diverse compounds with excellent enantioselectivity, and has been demonstrated in the synthesis of key chiral building blocks for bioactive compounds such as (+)-eptazocine and (-)-aphanorphine.
Article
Chemistry, Physical
Changhua Song, Hong-Hao Zhang, Shouyun Yu
Summary: In this study, a decarboxylative allylic benzylation catalyzed by Pd/photoredox in a regio- and enantioselective manner is achieved. This method uses readily available aryl acetic acids as benzylic nucleophile equivalents without preactivation. The mild and atom-economical protocol expands the scope of coupling partners of allylic electrophiles. Additionally, vinyl epoxides can undergo this transformation smoothly, producing various chiral homoallylic alcohols bearing all-carbon quaternary stereocenters.
Review
Chemistry, Inorganic & Nuclear
Jessica Margalef, Maria Biosca, Pol de la Cruz Sanchez, Jorge Faiges, Oscar Pamies, Montserrat Dieguez
Summary: The success of phosphine-oxazoline ligands has led to advancements in P-oxazoline ligand families, resulting in diverse structures and more efficient ligands for asymmetric transformations. Through proper design, these heterodonor bidentate ligand families exhibit superior catalytic performance in a variety of asymmetric reactions.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Xin Yu, Lingfei Hu, Wolfgang Frey, Gang Lu, Rene Peters
Summary: Catalytic allylic substitution is an important method in asymmetric synthesis to generate C-C bonds with enantioselectivity. However, a common limitation is the formation of allylic substitution products with (E)-configured C=C double bonds. In this study, a planar chiral palladacycle catalyst was used to achieve a diastereospecific reaction outcome, maintaining the C=C double bond geometry of the allylic substrates in highly enantioenriched products.
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, Organic
Jia Shihu, Chen Siyuan, Liu Zeshui, Cheng Honggang, Zhou Qianghui
Summary: A new type of axially chiral phosphine-alkene ligands have been developed for Pd-catalyzed asymmetric allylic alkylation of indoles via a two-step modular synthesis. The reaction provides a series of chiral allylindole products with generally high yields (up to 95%) and excellent enantioselectivities (up to 96% ee).
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Wei Tian, Bowen Li, Duanshuai Tian, Wenjun Tang
Summary: A palladium-catalyzed 2-alkylation of indoles with alpha-bromo esters using a P,P=O ligand has been developed. The method shows excellent regioselectivities, mild reaction conditions, and good functional group compatibility. Mechanistic studies indicate that the reaction proceeds through a radical pathway.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Sarah Kelly, Richard Goddard, Patrick J. Guiry
Summary: Two novel pyrazine-containing ligands were designed and synthesized, and showed high reactivity and selectivity in palladium-catalysed allylic alkylation reactions. The solution structures and dynamic behaviour of palladium complexes were elucidated by NMR spectroscopic experiments.
HELVETICA CHIMICA ACTA
(2022)
Review
Chemistry, Organic
Xinhui Yu, Ting Zhang, Jitian Liu, Xiaoxun Li
Summary: This short review summarizes recent developments in the synthesis of quaternary stereocenters via DAAA methods since 2018, showcasing its potential in organic and medicinal chemistry through representative examples of total synthesis of complex natural products.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Multidisciplinary
Wang Yao, Chuan-Jun Lu, Li-Wen Zhan, Yi Wu, Jia Feng, Ren-Rong Liu
Summary: In this study, a palladium-catalyzed enantioselective C-H activation method for pyrroles was reported, which successfully synthesized structurally diverse indole-pyrrole atropisomers with a chiral N-N axis, showing high yields and enantioselectivities. Furthermore, the kinetic resolution of trisubstituted N-N heterobiaryls with more sterically demanding substituents was also achieved. This versatile method enables the rapid and selective functionalization of pyrroles, facilitating the synthesis of valuable and complex N-N atropisomers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Biochemistry & Molecular Biology
Mohamed M. Hammoud, Muhammad Khattab, Marwa Abdel-Motaal, Johan Van der Eycken, Radwan Alnajjar, Hamada Abulkhair, Ahmed Ali Al-Karmalawy
Summary: In this article, a ferrocene derivative was synthesized through a series of five-step chemical reactions, and its structure was characterized. Molecular docking and molecular dynamics simulations revealed that the synthesized compound exhibited promising anticancer activity. Additionally, DFT calculations provided insights into the physicochemical properties of the derivative.
JOURNAL OF BIOMOLECULAR STRUCTURE & DYNAMICS
(2023)
Review
Chemistry, Multidisciplinary
Xiao Tang, Songtao Ding, Liangliang Song, Erik V. V. Van der Eycken
Summary: The isoindolo[2,1-b]isoquinolin-5(7H)-one scaffold is a widely found core structure in many bioactive natural products. Transition metal-catalyzed C-H activation/annulation has emerged as a powerful method to construct diverse polyheterocycles and has been employed for the synthesis of isoindolo[2,1-b]isoquinolin-5(7H)-one. This review provides an overview of recent advances in the preparation of isoindolo[2,1-b]isoquinolin-5(7H)-ones using transition metal-catalyzed C-H activation/annulation, aiming to help researchers discover hidden opportunities and accelerate the discovery of novel transformations based on C-H activation/annulation.
Article
Health Care Sciences & Services
Christiaan Vis, Josien Schuurmans, Bruno Aouizerate, Mette Atipei Craggs, Philip Batterham, Leah Buhrmann, Alison Calear, Arlinda Cerga Pashoja, Helen Christensen, Els Dozeman, Claus Duedal Pedersen, David Daniel Ebert, Anne Etzelmueller, Naim Fanaj, Tracy L. Finch, Denise Hanssen, Ulrich Hegerl, Adriaan Hoogendoorn, Kim Mathiasen, Carl May, Andia Meksi, Sevim Mustafa, Bridianne O'Dea, Caroline Oehler, Jordi Piera-Jimenez, Sebastian Potthoff, Gentiana Qirjako, Tim Rapley, Judith Rosmalen, Ylenia Sacco, Ludovic Samalin, Mette Maria Skjoth, Kristine Tarp, Ingrid Titzler, Erik Van der Eycken, Claire Rosalie van Genugten, Alexis Whitton, Enrico Zanalda, Jan H. Smit, Heleen Riper
Summary: This study compared the effectiveness of the ItFits-toolkit with implementation-as-usual in implementing iCBT services in routine mental health care organizations. The ItFits-toolkit performed better in supporting implementers in developing and applying effective tailored implementation strategies, but had a small effect on normalization levels among service providers.
JOURNAL OF MEDICAL INTERNET RESEARCH
(2023)
Review
Chemistry, Multidisciplinary
Xiao Tang, Liangliang Song, Erik V. Van Der Eycken
Summary: The Ugi reaction is highly explored due to its mild reaction conditions, wide scope, and high variability for the formation of multifunctional adducts. By carefully selecting the starting four components, Ugi-adducts can undergo different post-transformations to synthesize bioactive heterocycles, natural products, and macrocycles. Various post-Ugi transformations have been developed for constructing structurally novel polycycles, and this account summarizes important efforts for the synthesis of polycyclic N-heterocycles via post-Ugi cyclizations from the Van der Eycken laboratory onwards 2016. With the aid of transition metal catalysis and metal-free strategies, versatile polyheterocycles are prepared with high efficiency and step-economy.
Review
Chemistry, Multidisciplinary
Xianjun Xu, Ling Zhong, Huangdi Feng, Erik V. V. Van Der Eycken
Summary: The metal-free dearomatization reactions have proven to be a green and sustainable method for constructing spirocyclic, polycyclic, and heterocyclic scaffolds. This review focuses on recent advances in metal-free dearomatization reactions, including organo-catalyzed, oxidative, Bronsted acid- or base-promoted, photoredox-catalyzed, and electrochemical oxidation dearomatization reactions.
Article
Chemistry, Multidisciplinary
Laura Y. Vazquez-Amaya, Guglielmo A. Coppola, Erik V. Van der Eycken, Upendra K. Sharma
Summary: The popularity of microflow chemistry has significantly increased in the last 20 years, leading to a transition from macro-batch reactors to miniaturized flow devices among chemists. Microfluidics has established itself as not just a trend but a new, effective, and sustainable way of conducting chemistry in the field of organic chemistry, with continuous growth and evolution expected. This perspective highlights the use of innovative enhancing technologies applied to microflow reactors, as well as examples of complex integrated microsystems and scale-up technologies, showcasing microflow as a promising choice for the future.
Article
Chemistry, Organic
Monica Oliva, Viktoriia V. Chernobrovkina, Erik V. van der Eycken, Upendra Kumar Sharma
Summary: Photoredox catalysis has gained significant attention in the synthetic community due to its ability to form challenging C-C and C-heteroatom bonds under mild and sustainable conditions. Developing novel synthetic strategies and suitable technologies to overcome scale-up issues has become a primary focus. Continuous-flow reactors play a major role in increasing the efficiency and accessibility of photocatalyzed reactions. Recent interest in using boron species as radical precursors in photocatalyzed reactions has emerged, despite the challenges posed by the high oxidation potential of boronic acids. This Account highlights recent contributions to this field with a focus on applicability, selectivity, and scalability through continuous-flow methodology.
Article
Chemistry, Multidisciplinary
Fabian Raymenants, Tom M. Masson, Jesus Sanjose-Orduna, Timothy Noel
Summary: Despite existing limitations in synthetic methods targeting direct C-H functionalization, a new protocol using photocatalytic hydrogen atom transfer and gaseous carbon monoxide enables the regioselective C-H carbonylation of saturated hydrocarbons. Flow technology is crucial for high gas-liquid mass transfer rates, fast reaction kinetics, scalability, and safety.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Chao Liu, Johan Van Der Eycken, Erik V. Van Der Eycken
Summary: A novel method was developed for transition metal-free N-S bond cleavage and subsequent C-N bond activation of Ugi-adducts. Diverse primary amides and a-ketoamides were prepared in a rapid, step-economic, and highly efficient manner in two steps. This strategy offers excellent chemoselectivity, high yield, and functional-group tolerance. Primary amides derived from the pharmaceuticals probenecid and febuxostat were successfully prepared. This method provides a new environmentally friendly pathway for the simultaneous synthesis of primary amides and a-ketoamides.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Arina Y. Obydennik, Alexander A. Titov, Anna V. Listratova, Tatiana N. Borisova, Irina L. Sokolova, Victor B. Rybakov, Erik V. Van der Eycken, Leonid G. Voskressensky, Alexey V. Varlamov
Summary: In this study, 1-substituted 1-ethynyl-2-vinyldi- and tetrahydroisoquinolines were successfully subjected to [3,3]-sigmatropic rearrangement under microwave irradiation at 150 degrees Celsius in toluene, in the presence of nucleophiles (DMAP, triphenylphosphine and tetrahydrothiophene), yielding pyrrolo[2,1-b][3]benzazepines with good yields. The replacement of toluene with acetonitrile directed the rearrangement towards the formation of 7,11b-dihydro-6H-pyrido[2,1-a]isoquinolines.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Organic
Alisa A. Nevskaya, Anna D. Zinoveva, Erik V. van der Eycken, Leonid G. Voskressensky
Summary: This paper provides a review on the synthesis methodologies and applications of different indolizine derivatives, including thienoindolizines and indolizino[8,7-b]indoles. Indolizine nucleus is a privileged scaffold of various natural and synthetic molecules with significant biological activity. Fused-indolizines, such as thienoindolizines and indolizinoindoles, have attracted great interest due to their antitumor, antimicrobial, and enzyme inhibitor activity. The study summarizes the approaches to the synthesis, properties, and application of various indolizine derivatives, with a focus on recent articles on indolizines and indolizino[8,7-b]indoles, as well as a general review on thienoindolizine derivatives.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Luca Capaldo, Zhenghui Wen, Timothy Noel
Summary: Flow chemistry has revolutionized synthetic community by providing numerous possibilities. This review explores the benefits of microreactor technology and how it can enhance organic synthesis by revealing governing principles and unique reactivity. It serves as a field guide for those interested in diving into the world of flow chemistry.
Review
Chemistry, Multidisciplinary
Liangliang Song, Lingchao Cai, Lei Gong, Erik V. Van der Eycken
Summary: Copper-catalyzed enantioselective coupling reactions have been extensively studied for the rapid synthesis of chiral molecules. Despite progress in polar and radical mechanisms, the development of general and practical strategies for the regio-, enantio-, and diastereoselective assembly of stereogenic centers remains challenging. The integration of photocatalysis with asymmetric copper catalysis offers new reaction pathways and diverse chiral compounds, expanding the scope of radical chemistry. This review provides a summary of recent advances in photoinduced copper-catalyzed enantioselective coupling reactions, with a discussion on the mechanistic aspects.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
Dimitris I. Ioannou, Luca Capaldo, Jiri Sanramat, Joost N. H. Reek, Timothy Noel
Summary: Electrophotocatalysis plays a significant role in organic synthesis and has potential for scalability. This study introduces a new concept of a flow reactor that utilizes both photons and electrons simultaneously. The device is not only applicable for electrophotocatalysis, but also for purely electrochemical and photochemical reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Alexey A. Festa, Olga A. Storozhenko, Leonid G. Voskressensky, Erik V. van der Eycken
Summary: The use of visible light-promoted chemistry in halogenation and halofunctionalisation reactions has significant impact.
CHEMICAL SOCIETY REVIEWS
(2023)
