Catalytic Asymmetric Synthesis of Atropisomers Bearing Multiple Chiral Elements: An Emerging Field

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(3)

Опубликована: Ноя. 2, 2023

With the rapid development of asymmetric catalysis, demand for enantioselective synthesis complex and diverse molecules with different chiral elements is increasing. Owing to unique features atropisomerism, catalytic atropisomers has attracted a considerable interest from chemical science community. In particular, introducing additional elements, such as carbon centered chirality, heteroatomic planar helical into provides an opportunity incorporate new properties axially compounds, thus expanding potential applications atropisomers. Thus, it important perform transformations synthesize bearing multiple elements. spite challenges in transformations, recent years, chemists have devised powerful strategies under organocatalysis or metal synthesizing wide range enantioenriched Therefore, become emerging field. This review summarizes progress this field indicates challenges, thereby promoting horizon.

Язык: Английский

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Enantioselective C−H Functionalization Reactions under Gold Catalysis

Chemistry - A European Journal, Год журнала: 2022, Номер 28(20)

Опубликована: Янв. 11, 2022

Abstract Transition metal‐catalyzed enantioselective functionalization of ubiquitous C−H bonds has proven to be promising field as it offers the construction chiral molecular complexity in a step‐ and atom‐economical manner. In recent years, gold emerged an attractive contender for catalyzing such reactions. The unique reactivities selectivities offered by catalysts have been exploited access numerous asymmetric transformations based on gold‐catalyzed processes. Herein, this review critically highlights major advances discoveries made under catalysis which is accompanied mechanistic insights at appropriate places.

Язык: Английский

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Construction of Axially Chiral Arylpyrroles via Atroposelective Diyne Cyclization

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(23)

Опубликована: Март 30, 2023

Axially chiral biaryls widely exist in natural products and pharmaceuticals are used as ligands catalysts asymmetric synthesis. Compared to the well-established axially 6-membered biaryl skeletons, examples of 5-membered have been quite scarce, mono-substituted 3-arylpyrrole atropisomers not reported. Here, we disclose a copper-catalyzed atroposelective diyne cyclization for construction range arylpyrrole good excellent yields with generally enantioselectivities via oxidation X-H insertion vinyl cations. Importantly, this protocol only represents first synthesis atropisomers, but also constitutes example atropisomer Theoretical calculations further support mechanism cation-involved elucidate origin enantioselectivity.

Язык: Английский

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Enantioselective Assembly of Ferrocenes with Axial and Planar Chiralities via Palladium/Chiral Norbornene Cooperative Catalysis

JACS Au, Год журнала: 2023, Номер 3(2), С. 384 - 390

Опубликована: Янв. 19, 2023

The preparation of ferrocenes with both axial and planar chiralities poses a considerable challenge. Herein, we report strategy for the construction in ferrocene system via palladium/chiral norbornene (Pd/NBE*) cooperative catalysis. In this domino reaction, first established chirality is dictated by Pd/NBE* catalysis, while latter controlled preinstalled through unique axial-to-planar diastereoinduction process. This method exploits readily available ortho-ferrocene-tethered aryl iodides (16 examples) bulky 2,6-disubstituted bromides (14 as starting materials. Five- to seven-membered benzo-fused (32 are obtained one step constantly high enantioselectivities (>99% e.e.) diastereoselectivities (>19:1 d.r.).

Язык: Английский

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Sadphos as Adaptive Ligands in Asymmetric Palladium Catalysis

Accounts of Chemical Research, Год журнала: 2024, Номер unknown

Опубликована: Янв. 31, 2024

ConspectusPalladium catalysis, as one of the most important strategies in asymmetric synthesis, has continuously attracted attention organic chemists. With development chiral ligands, increasingly challenging reactions and substantial progress catalysis are being realized.Since 2014, we have focused on exploiting a series sulfinamide phosphine ligands called "Sadphos," including Ming-Phos, Xu-Phos, Xiao-Phos, Xiang-Phos, TY-Phos, PC-Phos, GF-Phos, WJ-Phos. These can be easily prepared two to four steps using commercial materials. new types shown remarkable performance transition-metal-catalyzed reactions, especially Pd-catalyzed transformations. X-ray diffraction analysis, mechanistic studies, density functional theory calculations revealed that Sadphos coordinate with Pd0 PdII species Pd0/P, Pd0/P,S, or PdII/P,O modes.This Account summarizes our recent efforts toward palladium-catalyzed enantioselective ligands. were found privileged very crucial promote by increasing reactivity enantioselectivity. Ming-Phos is an effective ligand coupling intramolecular Heck providing highly trisubstituted allenes, axially anilides, gem-diarylmethine silanes, disubstituted dihydroisoquinolinones. Incorporation electron-rich cyclohexyl group moiety afforded which showed unique effect transformations, reductive Heck, dearomative Mizoroki–Heck, tandem Heck/Suzuki coupling, carboiodination, carboamination, cross-coupling reactions. Using similar strategy, synthesized more electron–rich TY-Phos Xiang-Phos bearing t-butyl 1-adamantyl at P atoms, respectively. Regarding stereoelectronic features, these characteristic best choice satisfy requirements fluoroarylation gem-difluoroalkenes, intermolecular α-arylation aldehydes, carboetherification alkenyl oximes, carboheterofunctionalization 2,3-dihydrofurans. Compared aforementioned attractive features high nucleophilicity originating from CH2PPh2 ortho-substituent side aryl ring, presumably responsible for its efficiency. The Pd/Xiao-Phos catalyst system shows good secondary oxides, affording P-stereogenic products multiple molecular skeletons. modification basic backbone introducing xanthene skeleton motivated us design synthesize monophosphines, named PC-Phos GF-Phos. various arylation sulfenate anions, denitrogenative cyclization benzotriazoles, dearomatization indoles. practicability GF-Phos was validated three-component N-tosylhydrazones, halides, terminal alkynes, well N-tosylhydrazones vinyl iodides pendent amines. In addition, ferrocene-derived WJ-Phos employed Suzuki–Miyaura reaction, biaryl monophosphine oxides excellent enantiomeric excesses.

Язык: Английский

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Asymmetric gold catalysis enabled by specially designed ligands

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

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Enantioselective synthesis of molecules with multiple stereogenic elements

Chemical Society Reviews, Год журнала: 2024, Номер 53(22), С. 11165 - 11206

Опубликована: Янв. 1, 2024

This review explores the fascinating world of molecules featuring multiple stereogenic elements, unraveling different strategies designed over years for their enantioselective synthesis.

Язык: Английский

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Dirhodium-Catalyzed Asymmetric Transformations of Alkynes via Carbene Intermediates

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Янв. 31, 2025

ConspectusFunctionalization of alkynes is an established cornerstone organic synthesis. While numerous transition metals exhibit promising activities in the transformations via π-insertion or oxidative cyclometalation, Lewis π-acids offer a different approach. By coordinating with through π-bonding, facilitate nucleophilic addition, leading to formation alkenyl metal species. These species can undergo electron rearrangement generate carbenes, which are crucial intermediates for subsequent carbene transfer reactions. This reaction pathway provides versatile route alkyne functionalization, especially asymmetric manner. Although π-acid, gold(I), pioneered this mode, development variants remains challenging due linear coordination gold(I). Therefore, expanding range catalysts beyond gold(I) complexes other would further advances chiral molecule construction and exploration novel modes.In Account, we present concise review multifunctionalization dirhodium-catalyzed transformations, providing modulation strategies substrates plausible mechanisms. In aromatization-driven strategy, furanyl dirhodium generated from enynone, terminated by enantioselective intramolecular C-H insertion, cyclopropanation, aromatic substitution, Büchner reaction, giving dihydroindoles, dihydrobenzofurans, cyclopropane-fused tetrahydroquinolines, fluorenes, cyclohepta[b]benzofurans. The cap-tether strategy was developed study balance reactivity selectivity azo-enyne. gave first catalytic cycloisomerization azo-enyne, affording centrally axially isoindazole derivatives. synergistic activation i.e., EWG C-H···O interaction, introduced achieve enynes, cyclopropane-annulated bicyclic systems enynals. Benefiting these successes, difluoromethyl-substituted enynes were designed proven be effective substrates. With corresponding benzo-1,6-enynes as substrates, biscyclopropanation cascaded cyclopropanation/cyclopropenation achieved using dicarbene equivalents. Additionally, benzo-1,5-enynal vinyl carbene, reacted variety alkenes [2 + 1] cycloaddition, [4 3] formal allylation, spiro fused polycyclic heterocycles. Coupling desymmetrization, successfully diynals, constructing furan-fused dihydropiperidines alkyne-substituted aza-quaternary stereocenter. Notably, analyzing X-ray structures several dirhodium-alkyne π-complexes, together results DFT calculations control experiments, obtained evidence supporting making well-defined paddlewheel-like dirhodium(II) stand out among complexes. We anticipate that our research will significantly advance fields dirhodium, alkyne, chemistry.

Язык: Английский

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Rhodium(III)-Catalyzed Enantioselective C–H Activation/Annulation of Ferrocenecarboxamides with Internal Alkynes

ACS Catalysis, Год журнала: 2022, Номер 12(5), С. 3083 - 3093

Опубликована: Фев. 21, 2022

Efficient synthesis of planar chiral ferrocene-fused heterocyclic molecules is challenging in asymmetric synthesis. Herein, we report an enantioselective C–H activation/annulation ferrocenecarboxamides with internal alkynes promoted by CpRh(III) catalysis. Trisubstituted Cp-derived Rh complexes are found to be enabling catalysts, which lead a broad substrate scope good functional group compatibility. Planar pyridone products obtained high yields (up 90%) excellent enantioselectivity 99% ee). Combined experimental and computational studies support the proposed reaction mechanism.

Язык: Английский

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Kinetic resolution of planar chiral metallocenes using Rh-catalysed enantioselective C–H arylation

Nature Synthesis, Год журнала: 2022, Номер 2(1), С. 49 - 57

Опубликована: Окт. 24, 2022

Язык: Английский

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