Sadphos as Adaptive Ligands in Asymmetric Palladium Catalysis

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 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.

Language: Английский

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Pd-Catalyzed Enantioselective Three-Component Carboamination of 1,3-Cyclohexadiene

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(31), P. 21231 - 21238

Published: July 29, 2024

Asymmetric Pd-catalyzed three-component carboamination reactions of dienes to construct chiral cyclohexenylamines, which are great importance in many fields chemistry, have remained largely unexplored. Here, we demonstrate a highly enantio- and regioselective Pd/Ming-Phos-catalyzed 1,3-cyclohexadiene with readily available aryl iodides anilines for facile access diverse valuable cyclohexenylamines. The process shows excellent functional group tolerance, easy scalability, mild conditions. Moreover, mechanistic studies suggest that this reaction has first-order dependence on the concentration palladium catalyst aniline.

Language: Английский

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Enantioselective synthesis of isoxazolines bearing allenes by palladium-catalyzed carboetherification of β,γ-unsaturated ketoximes with propargylic acetates

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Enantioselective synthesis of isoxazolines bearing allenes by palladium catalyzed carboetherification alkenyl oximes with propargylic acetates. DFT calculations carried out to disclose the detailed mechanism and origins enantioselectivity.

Language: Английский

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Integrating Olefin Carboamination and Hofmann‐Löffler‐Freytag Reaction by Radical Deconstruction of Hydrazonyl N−N Bond

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(17)

Published: Feb. 21, 2024

As a type of elementary organic compounds containing N-N single bond, hydrazone involved chemical conversions are extremely extensive, but they mainly limited to N

Language: Английский

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Electroreductive Carboxylation of Propargylic Acetates with CO₂: Access to Tetrasubstituted 2,3-Allenoates

Organic Letters, Journal Year: 2023, Volume and Issue: 25(51), P. 9176 - 9180

Published: Dec. 19, 2023

An electroreductive carboxylation of propargylic alcohols with CO2 and then workup TMSCHN2 to construct tetrasubstituted 2,3-allenoates is developed. This method allows the incorporation an external ester group into resulting allene system through electroreduction, carboxylation, deacetoxylation cascades. Mechanistically, electricity on/off experiments cyclic voltammetry analysis support preferential generation radical anion or 3-aryl acetate based on electron nature aryl rings.

Language: Английский

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Synthesis of Multisubstituted Allenes by Palladium-Catalyzed Carboetherification of β,γ-Unsaturated Ketoximes with Propargylic Acetates

Organic Letters, Journal Year: 2023, Volume and Issue: 25(25), P. 4682 - 4687

Published: June 19, 2023

A highly efficient Pd-catalyzed carboetherification reaction of β,γ-unsaturated ketoximes with propargylic acetates is demonstrated. This method provides a practical protocol for accessing the incorporation an allene moiety into 3,5-disubstituted and 3,5,5-trisubstituted isoxazolines. The salient features this transformation include broad substrate scope, good functional group tolerance, easy scale-up, versatile transformations, applications in late-stage modification drugs.

Language: Английский

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Palladium-catalysed alleneamination of γ,δ-unsaturated hydrazones with propargylic acetates: access to tetrahydropyridazines bearing allenes

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Herein, we reported a palladium-catalysed alleneamination of γ,δ-unsaturated hydrazones with propargylic acetates, which provides an efficient approach for the synthesis tetrahydropyridazine bearing allenes in moderate to good yields.

Language: Английский

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The synthesis of isoxazolines and dihydrooxazines by Pd-catalyzed oxyalkynylation alkenyl oximes with alkynyl bromides

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(10), P. 2768 - 2773

Published: Jan. 1, 2024

Synthesis of isoxazolines and dihydrooxazines bearing an alkyne group by Pd-catalyzed oxyalkynylation alkenyl oximes with alkynyl bromides. This new approach has a broad substrate scope good functional tolerance.

Language: Английский

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Palladium-catalyzed selective C–C bond cleavage of keto-vinylidenecyclopropanes: construction of structurally rich dihydrofurans and tetrahydrofurans

Chemical Science, Journal Year: 2024, Volume and Issue: 15(24), P. 9192 - 9200

Published: Jan. 1, 2024

A series of bicyclic products containing dihydrofuran and tetrahydrofuran skeletons were obtained by divergent palladium-catalyzed selective C–C bond cleavage keto-VDCPs. The reaction mechanism was also investigated systematically.

Language: Английский

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Photoinduced [3+2] Cycloaddition of Alkyl–Acceptor Diazoalkanes: Diversity-Oriented Synthesis of Pyrazolines Containing a Quaternary Center

Organic Letters, Journal Year: 2024, Volume and Issue: 26(19), P. 4031 - 4036

Published: Jan. 26, 2024

We present a new [3+2] cycloaddition reaction between alkyl-acceptor diazoalkanes under visible light irradiation. By employing easily accessible alkyl-acceptor-type or their precursor hydrazones as both 1,3-dipoles and dipolarophiles, diverse range of pyrazoline derivatives featuring quaternary center have been efficiently synthesized in predictable manner, with excellent functional group tolerance good yields. Furthermore, scale-up experiments downstream transformations the product were also detailed.

Language: Английский

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