Review
Chemistry, Organic
Helene Pellissier
Summary: This review provides an overview of the recent developments in enantioselective nickel-catalyzed conjugate additions of various nucleophiles to acceptor-activated olefins since 2016. These reactions offer powerful and cost-effective methodologies for stereocontrolled formation of carbon-carbon and carbon-heteroatom bonds due to the lower costs of nickel catalysts compared to other transition metals. When utilized in domino reactions, these processes enable direct access to a variety of complex and functionalized chiral molecules.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Review
Chemistry, Multidisciplinary
Corinne Coutant, Paul De Bonfils, Pierrick Nun, Vincent Coeffard
Summary: The advent of asymmetric organocatalysis has revolutionized the way chemists create or break chemical bonds, enabling new strategies for enantioselective functionalization. This success is attributed to various activation modes and the availability of numerous chiral organic catalysts. Selective functionalization of compounds with multiple activation sites, such as cyclohexanone-derived dienones, has also contributed to breakthroughs in this field. These compounds can undergo diverse transformations and offer new opportunities for natural product synthesis. This review focuses on intermolecular functionalization of (cross)-conjugated cyclohexanone-derived compounds using asymmetric organocatalysis.
Article
Chemistry, Multidisciplinary
Nolan C. Turman, Kendrick L. Smith, Evan T. Crawford, Jacob G. Robins, Kathryn M. Weber, Shubin Liu, Jeffrey S. Johnson
Summary: Rhodium complexes catalyze the three-component coupling reaction, producing products with stereochemical diversity. The involvement of Rh-alkoxides in the Brook rearrangement has been confirmed. Furthermore, enantioselective products were obtained using chiral Rh-catalysts, with the best selectivity achieved using a specific ligand. The results of this study are of great significance for the synthesis of complex organic compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Analytical
Yujing Zuo, Zhiming Gou, Minggang Tian, Jingting Zhan, Weiying Lin
Summary: Rapid response is an important goal in fluorescence analysis technology, but it is often uncontrollable due to the limitations of the response mechanism and detection targets. In this study, a novel catalyst PNL-Br was synthesized and successfully incorporated into fluorescence analysis, showing a higher catalytic potential in thiol-Michael addition reactions. Notably, PNL-Br was an efficient catalyst for dithiothreitol (DTT) detection by fluorescence analysis, which was the first example of a catalysis system for fluorescent probe detection reactions.
SENSORS AND ACTUATORS B-CHEMICAL
(2023)
Article
Chemistry, Organic
Paula Oroz, Claudio D. Navo, Alberto Avenoza, Jesus H. Busto, Francisco Corzana, Gonzalo Jimenez-Oses, Jesus M. Peregrina
Summary: This research describes the diastereoselective 1,4-conjugate additions of anionic and radical C-nucleophiles to a chiral bicyclic dehydroalanine (Dha). Notably, radical carbon photolysis using a metal-free photocatalyst through a catalytic photoredox process provides exceptional yields and selectivities at room temperature. These 1,4-conjugate additions serve as an excellent starting point for synthesizing enantiomerically pure carbon-beta-substituted unnatural alpha-amino acids (UAAs), with potential applications in chemical biology.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Hao Xu, Yun-Xuan Tan, Pei-Pei Xie, Rui Ding, Qi Liao, Jian-Wei Zhang, Qing-Hua Li, Yu-Hui Wang, Xin Hong, Guo-Qiang Lin, Ping Tian
Summary: A rhodium(III)-catalyzed asymmetric reductive cyclization was reported for alpha,beta-unsaturated compounds tethered with cyclohexadienone, leading to cis-bicyclic frameworks with good yields and enantioselectivities. The role of ring strain in controlling regioselectivity and favoring 5,6-bicyclic products was also demonstrated by DFT calculations.
Article
Chemistry, Applied
Masahiro Sai, Hiroaki Kurouchi
Summary: In this study, the first KHMDS-catalyzed Michael additions of allylic alcohols to alpha,beta-unsaturated amides were reported. The reaction proceeds smoothly with only 5 mol% of KHMDS to afford a variety of 1,5-ketoamides in high yields. Mechanistic investigations revealed that the in-situ generation of the enolate from the allylic alcohol through a tunneling-assisted 1,2-hydride shift is crucial for the success of this transformation.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Biochemistry & Molecular Biology
Kalyan Dey, Narayanaswamy Jayaraman
Summary: This study reports a pyridoneimine-catalyzed oxa-Michael addition of protecting groups-free, native mono- and disaccharides with Michael acceptors in aqueous solution. The addition occurs with site-selectivity at the anomeric lactol, leading to the synthesis of keto-glycopyranoside products. These products can be further functionalized with amino acids through reductive amination. The method provides a facile way to conjugate mono- and disaccharides with amino acids.
CARBOHYDRATE RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Giuseppe Zuccarello, Suzanne M. Batiste, Hyungdo Cho, Gregory C. Fu
Summary: Due to increasing interest in the pharmaceutical industry, the synthesis of chiral alpha-aminoboronic derivatives has become an important challenge. In this study, we demonstrate the enantioselective synthesis of these derivatives using a chiral copper catalyst generated from commercially available components. Mechanistic studies were also conducted to optimize the process and provide insights into the reaction mechanism.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Biochemistry & Molecular Biology
Yuelin Xu, Fengxi Li, Jinglin Ma, Jiapeng Li, Hanqing Xie, Chunyu Wang, Peng Chen, Lei Wang
Summary: This study reveals a new biocatalytic strategy for the direct synthesis of organophosphorus compounds with C-P bonds. The strategy shows good functional group compatibility and practical operation, with potential broad applications in organic synthesis.
Article
Chemistry, Organic
Paula Oroz, Claudio D. Navo, Alberto Avenoza, Jesus H. Busto, Francisco Corzana, Gonzalo Jimenez-Oses, Jesus M. Peregrina
Summary: The study introduces a novel method for the chemo- and diastereoselective 1,4-conjugate additions of Se-nucleophiles to a chiral bicyclic dehydroalanine, offering a promising route for the synthesis of enantiomerically pure selenocysteine derivatives with high potential for chemical biology applications.
Article
Chemistry, Multidisciplinary
Yu-Jun Bai, Xue-Ying Wang, Si-Kai Zhu, Xiao-Hui Zheng, Sheng-Yong Zhang, Ping-An Wang
Summary: A highly chiral cyclopropenimine-catalyzed enantioselective Michael addition between benzophenone-imine of glycine esters and beta-substituted alpha,beta-unsaturated pyrazolamides has been realized to afford Michael adducts in up to 95% yield and 99% ee.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Physical
Sayed Mustafa Badr, Manel Azlouk, Erhan Zor, Haluk Bingol, Mustafa Durmaz
Summary: Heterogeneous asymmetric catalysis based on earth-abundant carbon materials is a promising alternative to metal-based catalysts. In this study, two new bifunctional carbocatalysts were prepared by anchoring organosilanes to graphene oxide, and their catalytic performances in asymmetric Michael addition reactions were investigated. The effects of solvents and additives were evaluated, and the catalysts showed good recyclability.
MOLECULAR CATALYSIS
(2022)
Article
Chemistry, Applied
Kenya Tamaribuchi, Jiaqi Tian, Kengo Akagawa, Kazuaki Kudo
Summary: Enantioselective Michael addition of beta-dicarbonyl compounds towards nitroalkenes was achieved using an immobilized, N-terminal-guanidinylated peptide catalyst. Various nucleophiles and electrophiles were employed, with the resin-supported catalyst being recyclable for five cycles. This method shows promise for industrial applications.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Jerson E. Lapetaje, Claire M. Young, Chang Shu, Andrew D. Smith
Summary: The isothiourea-catalyzed formal enantioselective conjugate addition of 2-hydroxybenzophenone imine derivatives to alpha,beta-unsaturated para-nitrophenyl esters has been developed, producing a range of beta-imino ester and amide derivatives in moderate to good isolated yields with excellent enantioselectivity. Electron-withdrawing substituents within the alpha,beta-unsaturated ester component are required for good product yield.
CHEMICAL COMMUNICATIONS
(2022)
