Catalytic Desymmetric Dicarbofunctionalization of Unactivated Alkenes

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(26)

Опубликована: Март 14, 2022

The construction of multi-stereocenters by a transition metal-catalyzed cross-coupling reaction is major challenge. catalytic desymmetric functionalization unactivated alkenes remains largely unexplored. Herein, we disclose -a dicarbofunctionalization 1,6-dienes via nickel-catalyzed reductive reaction. leverage the underdeveloped chiral 8-Quinox enables Ni-catalyzed carbamoylalkylation both mono- and disubstituted to form pyrrolidinone bearing two nonadjacent stereogenic centers in high enantio- stereoselectivitives with broad functional-group tolerance. synthetic application pyrrolidinones allows rapid access complex fused-heterocycles.

Язык: Английский

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Palladium-Catalyzed Asymmetric Dearomative Carbonylation of Indoles

Organic Letters, Год журнала: 2022, Номер 24(16), С. 3033 - 3037

Опубликована: Апрель 18, 2022

Herein, we disclose a strategy for the asymmetric dearomatization of N-arylacyl indoles via palladium-catalyzed tandem Heck/carbonylation, leading to an array indoline-3-carboxylates bearing vicinal C2-aza-quaternary and C3 tertiary stereocenters in high yields excellent enantio- diastereoselectivities. This study is important advance field carbonylation enantioselective reactions.

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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Ni-catalyzed carbamoylation of unactivated alkenes for stereoselective construction of six-membered lactams

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Окт. 10, 2022

Abstract Nitrogen-based heterocycles have aroused widespread interest due to their reoccurrence in many pharmaceuticals. Amongst these motifs, the enantioenriched lactams are ubiquitous scaffolds found myriad biologically active natural products and drugs. Recently, transition metal-catalyzed asymmetric carbamoylation has been widely employed as a straightforward arsenal for chiral lactam architecture synthesis, including β-lactam γ-lactam. However, despite extensive efforts, there still remains no protocol accomplish related δ-lactam synthesis. In this manuscript, Ni-catalyzed enantioselective of unactivated alkenes by leverage reductive dicarbofunctionalization strategy allows expedient access two types mostly common six-membered lactams: 3,4-dihydroquinolinones 2-piperidinone high yield enantioselectivity. This features with good functional group tolerance, well broad substrate scope. The newly developed 8-Quinox skeleton ligand is key parameter transformation, which significantly enhances reactivity

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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Enantioselective Synthesis of Hydrindanes via Palladium-Catalyzed Asymmetric Desymmetrization of Cyclohexadiene Derivatives

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 5, 2025

We herein disclose a strategy for the asymmetric desymmetrization of cyclohexadiene derivatives via palladium-catalyzed Heck and tandem Heck/Tsuji-Trost allylic alkoxylation reaction. By employing DCE as solvent, we obtained variety chiral hydrindanes containing an all-carbon quaternary carbon center tertiary in good yields with excellent enantioselectivities. With alcohols valuable one stereocenter two centers were constructed high level enantioinduction.

Язык: Английский

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Palladium-catalyzed 3,4-hydroaminocarbonylation of conjugated dienes for formation of β,γ-unsaturated amides

Science China Chemistry, Год журнала: 2023, Номер 66(5), С. 1474 - 1481

Опубликована: Апрель 17, 2023

Язык: Английский

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Synthesis of Chiral Polycyclic Indoles via Pd(II)-Catalyzed Sequential Cyclization and Carbonylation

ACS Catalysis, Год журнала: 2024, Номер 14(11), С. 8739 - 8747

Опубликована: Май 21, 2024

Asymmetric tandem Heck and carbonylation reactions provide an efficient route to synthesize biologically important chiral cyclic compounds with a carbonyl group have attracted increasing research interests. However, this type of reaction relies on the initiation from oxidative addition aryl halides or pseudo halides, resulting in low atomic economy reaction. In addition, protocol has not adequately demonstrated reactivity generality heteroarene halides. Meanwhile, asymmetric Wacker-type cyclization are plagued by narrow substrate scope enantioselectivity remain underexplored. Herein, we describe Pd(II)-catalyzed sequential 1,6-enynes analogues carbon monoxide (CO). This catalytic system tolerates broad nucleophiles, including phenols, alcohols, amines. sequence forms four chemical bonds, two rings, up three stereocenters single step. strategy allows for convenient access variety polycyclic good yields enantio- diastereoselectivities, indoles, benzofurans, indole- benzofuran-fused bicyclo[3.2.1]octanes, indole-fused bicyclo[4.2.1]nonane.

Язык: Английский

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Atroposelective carbonylation of aryl iodides with amides: facile synthesis of enantioenriched cyclic and acyclic amides

Organic Chemistry Frontiers, Год журнала: 2021, Номер 8(21), С. 6067 - 6073

Опубликована: Янв. 1, 2021

An unprecedented palladium-catalyzed asymmetric carbonylation of ArI with carbon monoxide (CO) to expand a class atroposelective cyclic and acyclic amides in good yields high enantioselectivities has been reported.

Язык: Английский

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Nickel-Catalyzed Asymmetric Reductive Dicarbamoylation of Alkenes

Organic Letters, Год журнала: 2021, Номер 23(16), С. 6407 - 6411

Опубликована: Авг. 4, 2021

Herein we report a nickel-catalyzed asymmetric reductive dicarbamoylation of alkenes, in which tethered carbamoyl chlorides and isocyanates serve as distinct electrophilic carbamoylating agents, providing new access to chiral oxindoles bearing an amide-substituted quaternary stereogenic center.

Язык: Английский

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