Design and Synthesis of Planar-Chiral Oxazole–Pyridine N,N-Ligands: Application in Palladium-Catalyzed Asymmetric Acetoxylative Cyclization

ACS Catalysis, Год журнала: 2023, Номер 13(14), С. 9829 - 9838

Опубликована: Июль 11, 2023

The development of chiral ligands to fine-tune the stereocontrol has been recognized as a crucial pillar asymmetric catalysis. In contrast well-developed pyridine–pyridine-type and pyridine–oxazoline-type ligands, oxazole–pyridine-type have rarely exploited. this study, class [2.2]paracyclophane-based planar-chiral oxazole–pyridine N,N-ligands designed synthesized. These presented superior performance in enantioselective palladium-catalyzed acetoxylative cyclization alkyne-tethered cyclohexadienones, providing cis-hydrobenzofurans that belong bioactive molecules with potent NF-κB inhibition broad substrate scope. results demonstrated promising potential an efficient type N,N-ligand scaffold.

Язык: Английский

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Nickel‐Catalyzed Enantioselective Reductive Alkyl‐Carbamoylation of Internal Alkenes

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(36)

Опубликована: Июль 12, 2022

Herein, we leverage the Ni-catalyzed enantioselective reductive dicarbofunctionalization of internal alkenes with alkyl iodides to enable synthesis chiral pyrrolidinones bearing vicinal stereogenic centers. The application newly developed

Язык: Английский

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Nickel/Quinim Enabled Asymmetric Carbamoyl‐Acylation of Unactivated Alkenes

Chinese Journal of Chemistry, Год журнала: 2023, Номер 41(14), С. 1673 - 1678

Опубликована: Фев. 14, 2023

Comprehensive Summary Transition metal‐catalyzed difunctionalization of tethered alkene has emerged as a prevailing tool for the expedient construction synthetically valuable cyclic compounds. However, most efforts have been devoted to reaction styrene‐type substrates due their rigid scaffold and high reactivity. With respect nonaromatic olefin, especially mono‐substituted alkene, still remains largely underdeveloped. Herein, we disclose nickel/Quinim complex TBADT‐cocatalyzed asymmetric carbamoyl‐acylation unactivated on carbamoyl chlorides with diverse aldehydes. The exhibits broad substrate scope good functional group tolerance, well efficiency enantioselectivity. Both monosubstituted 1,1‐substituted alkenes can work either aliphatic or aromatic aldehydes under current protocol, providing convenient access an array medicinally useful chiral γ‐lactams derivatives bearing convertible acyl functionality. This showcases more application possibilities Quinim ligand in future catalytic transformations.

Язык: Английский

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Nickel-Catalyzed Asymmetric Cross-Electrophile trans-Aryl-Benzylation of α-Naphthyl Propargylic Alcohols

ACS Catalysis, Год журнала: 2023, Номер 13(10), С. 6795 - 6803

Опубликована: Май 3, 2023

Herein, we report a nickel-catalyzed asymmetric three-component trans-dicarbofunctionalization of β-substituted α-naphthyl propargylic alcohols using readily available aryl and benzyl halides as the coupling partners under reductive conditions. This cross-electrophile strategy enables synthesis various axially chiral allylic bearing tetrasubstituted olefinic unit in complete regio- E selectivity, well high enantiocontrol. Relying on hydroxyl group functional handle, such structural motifs are successfully derivatized into diverse functional-group-rich alkenes.

Язык: Английский

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Synthesis of Multisubstituted Allenes via Nickel-Catalyzed Cross-Electrophile Coupling

ACS Catalysis, Год журнала: 2021, Номер 11(21), С. 13355 - 13362

Опубликована: Окт. 19, 2021

In this context, we report the successful application of a cross-electrophile strategy in synthesis multisubstituted allenes. Under catalysis nickel, reductive cross-coupling between propargyl carbonates and organoiodides provides an entry to prepare tri- or tetrasubstituted allenes without employing any pregenerated organometallics. Furthermore, also prove be suitable allenylating agents nickel-catalyzed asymmetric aryl-allenylation aryl-iodide-tethered unactivated alkenes, furnishing variety chiral benzene-fused cyclic compounds bearing quaternary allenyl-substituted stereogenic center highly enantioselective manner.

Язык: Английский

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Cobalt-Catalyzed Asymmetric Reductive Dicarbofunctionalization of 1,3-Dienes with o-Bromoaryl Imines as a Bis-Electrophile

ACS Catalysis, Год журнала: 2022, Номер 13(1), С. 744 - 748

Опубликована: Дек. 23, 2022

Herein, we report a cobalt-catalyzed asymmetric reductive 1,2-dicarbofunctionalization of 1,3-dienes employing o-bromoaryl imines as bis-electrophilic coupling partner. This method provides an entry to prepare disubstituted cis-indanes in high diastereo- and enantioselectivities under mild reaction conditions. The proposed mechanism consists enantioselective intermolecular migratory insertion diastereoselective intramolecular allylation the key elementary steps.

Язык: Английский

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Nickel-Catalyzed Arylcarbamoylation of Alkenes of N-(o-Iodoaryl)acrylamides with Nitroarenes via Reductive Aminocarbonylation: Facile Synthesis of Carbamoyl-Substituted Oxindoles

Organic Letters, Год журнала: 2021, Номер 23(24), С. 9543 - 9547

Опубликована: Дек. 3, 2021

Nickel-catalyzed arylcarbamoylation reactions of alkenes N-(o-haloaryl)acrylamides with CO and nitroarenes via reductive aminocarbonylation to produce carbamoyl-substituted oxindoles an all-carbon quaternary stereogenic center are presented. Starting N-(o-haloaryl)acrylamides, simple CO, inexpensive using a Ni catalyst, dinitrogen-based ligand, Zn reductant, TMSCl additive, base system, this protocol enables the synthesis various allows efficient late-stage derivatization valuable molecules.

Язык: Английский

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Nickel‐Catalyzed Intramolecular Alkene Difunctionalization by Ball‐Milling

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(9), С. 1477 - 1484

Опубликована: Апрель 14, 2023

Abstract A mechanochemical nickel‐catalyzed intramolecular difunctionalization reaction of alkene tethered aryl halides with alkyl is herein described. This method allows for synthesis 3,3‐disubstituted heterocycles, namely oxindoles, shorter times than solution‐phase counterparts. Additionally, this process solvent minimized, DMA used in liquid‐assisted grinding (LAG) quantities and circumvents the need chemical activation terminal reductant (manganese) through mechanical grinding. The can be scaled up to yield over a gram product modest enantioinduction possible by utilizing chiral PyrOx ligand. magnified image

Язык: Английский

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Recent Advances in Nickel Catalyzed Asymmetric Acylation Reactions

Chinese Journal of Organic Chemistry, Год журнала: 2023, Номер 43(3), С. 1023 - 1023

Опубликована: Янв. 1, 2023

Chiral α-carbonyl compounds are important structural units in natural products and pharmaceuticals versatile synthetic building blocks organic synthesis.Transition metal-catalyzed asymmetric acylation reaction is one of the most straightforward methods for preparing these compounds.In particular, significant progress has been made area nickel-catalyzed reaction, due to unique properties nickel catalysts.The latest including alkyl-acyl cross-coupling hydroacylation alkene acyl-functionalization alkene, summarized.

Язык: Английский

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Pd/NBE-Catalyzed One-Pot Modular Synthesis of Polycyclic Fused δ-Lactams and Investigation of Room-Temperature Phosphorescence

ACS Catalysis, Год журнала: 2024, Номер 14(16), С. 12181 - 12191

Опубликована: Июль 30, 2024

The advancement of sophisticated synthetic methodologies that streamline reaction processes while enhancing molecular complexity is a perpetual necessity in the realm chemistry. Catalytic one-pot cascade play crucial role efficient construction intricate molecules with exceptional chemoselectivity. Herein, we present approach for synthesis polycyclic fused δ-lactams via sequential phosgenation, Pd/NBE-catalyzed ortho-carbamoylation/ipso-Heck-type cyclization, and C–H activation from readily available aryl halides, amines, triphosgenes. This stands out as first example situ carbamoyl chloride formation amine precursors, presenting an alternative to existing transformations involving chlorides. practical significance these showcased by 81 rapid economically favorable manner, without need intermediate purification. Moreover, were scalable compatible various natural products pharmaceuticals, further underscoring effectiveness this strategy. relatively rigid coplanar structure displayed our synthesized exhibits distinct room-temperature phosphorescence characteristics, which have been utilized anticounterfeiting high-security-level data encryption.

Язык: Английский

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