Recent advances in Pd-catalyzed asymmetric cyclization reactions

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 53(2), P. 883 - 971

Published: Dec. 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.

Language: Английский

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Direct Catalytic Asymmetric and Regiodivergent N1‐ and C3‐Allenylic Alkylation of Indoles

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(21)

Published: March 21, 2023

Herein we report a Pd-catalyzed asymmetric allenylic alkylation strategy for the direct functionalization of 1H-indoles by employing P-chiral BIBOP-type ligands. The regioselectivity (N1/C3) this process can be switched efficiently. Using Cs2 CO3 at elevated temperatures in MeCN, N1-alkylated indoles bearing axial chirality with stereocenter non-adjacent (β) to nitrogen are produced good yields high enantioselectivity and complete N1-regioselectivity regardless electronic properties substitution patterns diverse indoles. K2 room temperature CH2 Cl2 , chiral C3-alkylated also obtained. Notably, introduce new class tri-substituted electrophiles that proceeded through different pathways from di-substituted electrophiles.

Language: Английский

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Transition‐Metal‐Catalyzed Cycloaddition Reactions to Access Seven‐Membered Rings

Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 26(67), P. 15354 - 15377

Published: July 24, 2020

Abstract The efficient and selective synthesis of functionalized seven‐membered rings remains an important pursuit within synthetic organic chemistry, as this motif appears in numerous drug‐like molecules natural products. Use cycloaddition reactions attractive approach for their construction the perspective atom step economy. Additionally, ability to combine multiple components a single reaction has potential allow combinatorial strategies diversity‐oriented synthesis. inherent entropic penalty associated with achieving these transformations impressively been overcome development catalysis, whereby can be pre‐organized through activation by transition‐metal‐catalysis. fine‐tuning metal/ligand combinations well conditions allows chemo‐, regio‐, diastereo‐ enantioselectivity transformations. Herein, we discuss recent advances transition‐metal‐catalyzed via combination 2–4 mediated variety metals. An emphasis is placed on mechanistic aspects both illustrate state science highlight unique application novel processes transition‐metals

Language: Английский

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Direct access to spirocycles by Pd/WingPhos-catalyzed enantioselective cycloaddition of 1,3-enynes

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: Sept. 27, 2021

Abstract Spirocycles play an important role in drug discovery and development. The direct, catalytic, enantioselective synthesis of spirocycles from readily available starting materials atom economic manner remains a highly sought-after task organic synthesis. Herein, Pd-hydride-catalyzed cycloaddition method for the spirocyclic compounds directly two classes commonly materials, 1,3-enynes cyclic carbon−hydrogen (C−H) bonds, is reported. reactions employ chiral Pd/WingPhos catalyst to both suppress formation bis-allenyl by-products control stereoselectivity. 1,3-Enynes are used as dielectrophilic four-carbon units reactions, which also enables enyne substrate-directed enantioselectivity switch with good levels stereocontrol. present spirocycle tolerates broad range functional groups 1,3-enyne substrates, including alcohols, esters, nitriles, halides, olefins. A variety diverse nucleophiles, pharmaceutically heterocycles carbocycles, can be flexibly incorporated spiro scaffolds.

Language: Английский

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Palladium‐Catalyzed Asymmetric [4+3]‐Cyclization Reaction of Fused 1‐Azadienes with Amino‐trimethylenemethanes: Highly Stereoselective Construction of Chiral Fused Azepines

Chinese Journal of Chemistry, Journal Year: 2019, Volume and Issue: 38(2), P. 151 - 157

Published: Nov. 20, 2019

Summary of main observation and conclusion A Pd‐catalyzed asymmetric aromative [4+3]‐cyclization reaction amino‐trimethylenemethanes (TMM, 1,3‐dipoles) with fused 1‐azadienes has been developed. This method enables access to the synthetically importance biologically active benzofuran azepines indeno‐azepines in excellent efficiency stereoselectivity (up 95% yield, 99% ee, >19 : 1 dr).

Language: Английский

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Copper-catalyzed asymmetric [4 + 1] annulation of yne-allylic esters with pyrazolones

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: unknown, P. 110114 - 110114

Published: June 1, 2024

Language: Английский

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Asymmetric Synthesis of Isoxazol-5-ones and Isoxazolidin-5-ones

Synthesis, Journal Year: 2020, Volume and Issue: 53(01), P. 107 - 122

Published: Oct. 12, 2020

Abstract Isoxazol-5-ones and isoxazolidin-5-ones represent two important classes of heterocycles, with several applications as bioactive compounds versatile building blocks for further transformations. Unlike the parent aromatic isoxazoles, presence one or stereocenters in ring renders their asymmetric construction particularly important. In this review, starting from description general features differences between these related compound families, we present an overview on most enantioselective synthesis strategies to access heterocycles. Both chiral metal catalysts organocatalysts have recently been successfully employed task some promising approaches will be discussed. 1 Introduction 2 Nucleophiles 2.1 C-Nucleophiles 2.2 N-Nucleophiles 2.3 Cyclization Processes 3 Asymmetric Construction Isoxazolidin-5-ones 3.1 Enantioselective α-Functionalizations 4 Arylideneisoxazol-5-ones Conjugated Addition 5 Conclusions

Language: Английский

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Palladium-catalyzed [4 + 3] dearomatizing cycloaddition reaction of N-iminoquinolinium ylides

Organic Chemistry Frontiers, Journal Year: 2020, Volume and Issue: 7(18), P. 2612 - 2617

Published: Jan. 1, 2020

An efficient approach to obtain saturated seven-membered ring containing three heteroatoms has been developed by using a palladium-catalyzed [4 + 3] dearomatizing cycloaddition. This features mild conditions and good functional group tolerance.

Language: Английский

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Pd-catalyzed cascade cyclization of allenylethylene carbonates and indandiones: Synthesis of tetracyclic dihydrocyclopentaindenofuranone derivatives

Chinese Chemical Letters, Journal Year: 2023, Volume and Issue: 34(10), P. 108297 - 108297

Published: March 6, 2023

Language: Английский

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Palladium-Catalyzed Asymmetric Trifluoromethylated Allylic Alkylation of Pyrazolones Enabled by α-(Trifluoromethyl)alkenyl Acetates

Organic Letters, Journal Year: 2021, Volume and Issue: 23(15), P. 5804 - 5808

Published: July 19, 2021

The first asymmetric trifluoromethylated allylic alkylation of pyrazolones using α-(trifluoromethyl)alkenyl acetates as a novel allylation reagent is described, affording various functionalized chiral containing allyl substituent in high yields with excellent regio-/enantio-/diastereoselectivities. Mechanistically, the double-bond migration presence 1,8-diazabicyclo[5.4.0]undec-7-ene initial and interesting step. More importantly, this study significance providing widely applicable trifluoromethyl-containing reagent.

Language: Английский

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