Tetrahedron Letters, Год журнала: 2022, Номер 112, С. 154221 - 154221
Опубликована: Окт. 31, 2022
Язык: Английский
Journal of the American Chemical Society, Год журнала: 2022, Номер 144(8), С. 3497 - 3509
Опубликована: Фев. 9, 2022
A new strategy for enantioselective transition-metal catalysis is presented, wherein a H-bond donor placed on the ligand of cationic complex allows precise positioning chiral counteranion responsible asymmetric induction. The successful implementation this paradigm demonstrated in 5-exo-dig and 6-endo-dig cyclizations 1,6-enynes, combining an achiral phosphinourea Au(I) chloride with BINOL-derived phosphoramidate Ag(I) salt thus allowing first general use anions Au(I)-catalyzed reactions challenging alkyne substrates. Experiments modified complexes anions, 1H NMR titrations, kinetic data, studies solvent nonlinear effects substantiate key H-bonding interaction at heart catalytic system. This conceptually novel approach, which lies intersection metal catalysis, organocatalysis, counterion-directed provides blueprint development supramolecularly assembled ligands complexes.
Язык: Английский
Процитировано
56
Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(6), С. 1220 - 1268
Опубликована: Янв. 22, 2024
Abstract Elaborated molecular architectures, specifically those bearing one or more carbon stereocenters, stand as an important class of carbocyclic and heterocyclic frameworks because they are frequently occurring core structures in numerous natural products biologically active pharmaceutical molecules. Over the past few decades, development versatile synthetic approaches via cascade cyclization reactions 1,6‐enynes for construction a series fused spiro compounds has been focus great deal research initiatives. These synthesis strategies peculiarly fascinating context assembly wide array molecules, products, agrochemicals, functional materials. In this review, recent developments transformations with diverse coupling reagents summarized since 2018, which could be divided into five categories: 1) Introduction; 2) Transition metal catalyzed 1,6‐enynes; 3) Metal‐free 4) Visible‐light‐induced 5) Electrocatalytic 1,6‐enynes.
Язык: Английский
Процитировано
13
Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(6), С. 1858 - 1895
Опубликована: Янв. 1, 2024
This review is planned to provide a comprehensive overview of the progress made in design and development chiral ligands for asymmetric gold catalysis.
Язык: Английский
Процитировано
13
The Chemical Record, Год журнала: 2025, Номер unknown
Опубликована: Янв. 28, 2025
Abstract Since the introduction of concept inherent chirality by Böhmer, an important part research focused on asymmetric synthesis calixarene macrocycles. However, long synthetic procedures and tedious separation strategies hampered application this technology in many topics organic chemistry, including enantioselective molecular recognition catalysis. Very recently, a new generation catalytic methodologies has been reported, able to provide highly functionalized, inherently chiral calixarenes straightforward manner. In review, we will discuss these methods versatile properties such macrocycles that call for potential applications areas science.
Язык: Английский
Процитировано
1
ChemPlusChem, Год журнала: 2021, Номер 86(9), С. 1283 - 1296
Опубликована: Июль 12, 2021
Abstract Gold(I) catalysts are ideal for the activation of alkynes under very mild conditions. However, unlike allenes or alkenes, triple bond cannot be prochiral. In addition, linear coordination displayed by gold(I) complexes places chiral ligand far away from substrate resulting in an inefficient transfer information. This poses a significant challenge achievement high enantiocontrol gold(I)‐catalyzed reactions alkynes. Although considerable progress on enantioselective transformations has recently been achieved, asymmetric non‐prochiral alkyne‐containing small molecules still represents great challenge. Herein we summarize recent advances intra‐ and intermolecular involving alkynes, discussing new designs that lie at basis these developments. We also focus mode action catalysts, their possible limitations towards next‐generation more efficient designs. Finally, square planar gold(III) complexes, which offer alternative to discussed.
Язык: Английский
Процитировано
55
Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(17), С. 9339 - 9344
Опубликована: Фев. 12, 2021
Chiral gold(I)-cavitand complexes have been developed for the enantioselective alkoxycyclization of 1,6-enynes. This cyclization has applied first total synthesis carbazole alkaloid (+)-mafaicheenamine C and its enantiomer, establishing configuration as R. The cavity effect was also evaluated in cycloisomerization dienynes. A combination experiments theoretical studies demonstrates that gold(I) forces enynes to adopt constrained conformations, which results high observed regio- stereoselectivities.
Язык: Английский
Процитировано
44
Chem, Год журнала: 2024, Номер 10(11), С. 3323 - 3341
Опубликована: Июль 5, 2024
Cavitands have emerged as privileged architectures in supramolecular chemistry. Nonetheless, achieving structural diversity and tunability through heterofunctionalization along the rims of macrocycles has remained a formidable challenge. As rudimental example, stepwise conversion C4v-symmetric scaffolds to inherently chiral ABCD patterns is synthetically impractical owing low theoretical yields (0.8%) need for chromatographic enantioseparation.Herein, we report catalytic desymmetrization strategy access cavitands. Through engineering ionic palladium catalysts, diverse functionalities, including aryl, alkenyl, alkynyl, amino groups, can be installed on large with high site- stereoselectivity. An adaptable protocol been established furnish designer ABCD-type cavitands accordance choreography coupling partners. Experimental computational studies reveal synergistic electrostatic steering catalysis by catalyst–substrate interactions.
Язык: Английский
Процитировано
8
ChemCatChem, Год журнала: 2022, Номер 14(14)
Опубликована: Май 2, 2022
Abstract The 1, n ‐enynes are potent scaffolds in organic synthesis, providing a state‐of‐the‐art approach for synthesizing various acyclic and carbo‐ heterocyclic compounds. Radical cascade cyclization C−H functionalization of have gained immense attention the synthetic community. Significant advancement this field has been developed over years, employing harsh expensive metal catalysts usually associated with intense product purification unwanted side‐products. In context, advent visible light photocatalysis as mild efficient area is welcome step. Herein, we provide an exclusive overview recent developments light‐assisted manipulation ‐enynes. We classified review into 1,3‐, 1,4‐, 1,5‐, 1,6‐, 1,7‐, 1,8‐enynes, well dienyne, enediyne‐based reactions.
Язык: Английский
Процитировано
24
Natural Product Reports, Год журнала: 2024, Номер 41(7), С. 1091 - 1112
Опубликована: Янв. 1, 2024
This review highlights a curated selection of publications utilizing homogeneous gold-catalyzed cycloaddition and cyclization reactions for the total synthesis natural products reported from 2016 to mid-2023.
Язык: Английский
Процитировано
6
Chemistry - An Asian Journal, Год журнала: 2022, Номер 17(24)
Опубликована: Окт. 18, 2022
Gold catalysis is an extremely enthusiastic field of investigation in the area. The development alternative, highly inventive, precompetitive techniques based on gold has paved way for executing a broad spectrum chemical transformations from uncomplicated starting materials. total synthesis natural products complex and more complicated task. An amalgamation product through gold-catalysis been thought-provoking job. protocol solved several problems related to numerous products. Thus, this review outlined some most notable benchmarks last seven years (2015-2021) their application strategy acquired by authors accomplish will be elaborately discussed emphasizing role gold-catalyzed reactions.
Язык: Английский
Процитировано
22