Recent advances in Pd-catalyzed asymmetric cyclization reactions

Chemical Society Reviews, Год журнала: 2023, Номер 53(2), С. 883 - 971

Опубликована: Дек. 18, 2023

This review aims to collect advancements in enantioselective palladium-catalyzed cyclization reactions over the past eleven years, and it is organized into thirteen sections depending on different types of transformations involved.

Язык: Английский

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Recent advances of Pd-π-allyl zwitterions in cycloaddition reactions

Chinese Chemical Letters, Год журнала: 2023, Номер 34(11), С. 108401 - 108401

Опубликована: Март 30, 2023

Язык: Английский

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Asymmetric Auto‐Tandem Palladium Catalysis for 2,4‐Dienyl Carbonates: Ligand‐Controlled Divergent Synthesis

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(17)

Опубликована: Фев. 14, 2022

Developing new asymmetric auto-tandem catalysis processes, especially in a divergent manner, is highly attractive but extremely challenging. Presented herein palladium-catalyzed reaction between 2,4-dienyl carbonates and o-TsNH arylimines or trifluoroacetophenones that proceeds through consecutive N-allylation, vinylogous addition, π-σ-π isomerization, another N-allylation sequence. Importantly, switchable diastereodivergent synthesis could be achieved by tuning the chiral bisphosphine ligands, which led to construction of broad spectrum fused tetrahydroquinoline architectures with moderate excellent enantioselectivity. Ligand control even enabled effective access regiodivergent azetidine chemodivergent β-H elimination fair enantioselectivity, further showing versatility current catalysis.

Язык: Английский

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Recent advances in ligand-enabled palladium-catalyzed divergent synthesis

Organic & Biomolecular Chemistry, Год журнала: 2023, Номер 22(1), С. 37 - 54

Опубликована: Ноя. 27, 2023

Developing efficient and straightforward strategies to rapidly construct structurally distinct diverse organic molecules is one of the most fundamental tasks in synthesis, drug discovery materials science. In recent years, divergent synthesis functional from same starting has attracted significant attention been recognized as an powerful strategy. To achieve this objective, proper adjustment reaction conditions, such catalysts, solvents, ligands, etc., required. review, we summarized efforts chemo-, regio- stereodivergent reactions involving acyclic cyclic systems catalyzed by palladium complexes. Meanwhile, types, including carbonylative reactions, coupling cycloaddition well probable mechanism have also highlighted detail.

Язык: Английский

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Transition Metal-Catalyzed Asymmetric Cyclizations Involving Allyl or Propargyl Heteroatom-Dipole Precursors

Chinese Journal of Organic Chemistry, Год журнала: 2022, Номер 42(10), С. 3051 - 3051

Опубликована: Янв. 1, 2022

Chiral heterocyclic compounds are an important class of chiral substances, which widespread in many drugs, pesticides and catalysts.Therefore, the efficient asymmetric synthesis these becomes a research hotspot organic synthesis.Transition metal-catalyzed cyclization with heteroatom-dipole precursors is method to construct frameworks.Among them, designed based on transition allyl or propargyl substitutions have been extensively studied past two decades occupied role this field.The cyclizations introduced detail.The advantages existing problems current methods analyzed, would provide useful reference for researchers related fields.

Язык: Английский

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Rigid P-Chiral Phosphorus Ligands for Highly Selective Palladium-Catalyzed (4+2) and (4+4) Annulations

Organic Letters, Год журнала: 2022, Номер 24(50), С. 9205 - 9209

Опубликована: Дек. 12, 2022

We developed novel shackled P-chiral ligands based on 1-phosphanorbornenes and oxazolines. They were subsequently evaluated in palladium-catalyzed (4+2) annulations, producing enantioenriched tetrahydropyran scaffolds good yields with high site selectivity enantioselectivity. Moreover, chemoselective (4+4) products also achieved by using acyclic imines. In addition, density functional theory calculations performed to afford the energy profile of Michael addition step ring formation step. This demonstrated that enantioselective annulations reaction between mostly under thermodynamic control.

Язык: Английский

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Synthesis of Polycyclic Imidazolidinones via Cascade [3 + 2]-Annulation of β-Oxo-acrylamides with Cyclic N-Sulfonyl Imines

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(22), С. 15805 - 15816

Опубликована: Окт. 31, 2023

An Et3N-catalyzed cascade [3 + 2]-annulation of β-oxo-acrylamides with cyclic N-sulfonyl ketimines or sulfamate-derived imines is developed under mild reaction conditions, which provides a concise and efficient route to access valuable sultam- sulfamidate-fused imidazolidinone derivatives in good excellent yields (80–95% yields) diastereoselectivities (>20:1 drs). The current protocol features atom economy, transition-metal-free process, broad functional group tolerance. Moreover, the asymmetric variant 2]-cycloaddition was achieved presence diphenylethanediamine quinine-based bifunctional squaramide organocatalysts C-1 C-11, giving corresponding chiral polycyclic imidazolidinones 68–90% 25–94% ees >20:1 drs all cases.

Язык: Английский

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Cooperative Pd/Chiral Secondary Amine Enabled Diastereo- and Enantioselective [3 + 2] Cycloannulation: Synthesis of Polysubstituted Cyclopentanes

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 17, 2025

A cooperative palladium/chiral amine enabled diastereo- and enantioselective [3 + 2] cycloaddition of π-allyl 1,3-dipoles with α,β-unsaturated aldehydes has been developed. series highly functionalized cyclopentanes bearing three continuous tertiary stereocenters can be facilely efficiently obtained in good to excellent yields (51-97%) synthetically useful enantioselectivity (93-99% ee) under mild reaction conditions. Control experiments HRMS analyses were conducted elucidate the possible mechanism. The utility current method was demonstrated by gram-scale synthesis elaboration products into various cyclopentanes.

Язык: Английский

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Cyclohepta[b]indole Core Construction via the Michael Addition/Friedel–Crafts Condensation Sequence

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Март 16, 2025

An approach to cyclohepta[b]indoles via the formal (4 + 3) annulation of readily synthesized 2-indolyl-derived 1,3-dicarbonyl compounds acrolein and enones was developed. The process is initiated by catalytic Michael addition, wherein adduct generated in situ. subsequent addition a Bro̷nsted acid catalyst triggers cascade that includes intramolecular Friedel–Crafts hydroxylalkylation followed dehydration. reaction relatively undemanding since even degrading chloroform able initiate it. obtained tetrahydrocyclohepta[b]indoles were prone toward easy dimerization, underscoring high reactivity double bond seven-membered ring.

Язык: Английский

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Palladium-catalyzed [6 + 4] cycloaddition with π-allyl all-carbon 1,6-dipole for the synthesis of ten-membered heterocycles

Organic Chemistry Frontiers, Год журнала: 2023, Номер 11(5), С. 1299 - 1304

Опубликована: Дек. 25, 2023

This work introduces a novel α,α-diester-δ-vinylvalerolactone as dipolar precursor in palladium-catalyzed [6 + 4] cycloaddition reaction with azadienes, resulting the production of ten-membered heterocycles.

Язык: Английский

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