Recent Advances in the Catalytic Asymmetric Friedel–Crafts Reactions of Indoles

ACS Omega, Journal Year: 2022, Volume and Issue: 7(40), P. 35446 - 35485

Published: Oct. 3, 2022

Functionalized chiral indole derivatives are privileged and versatile organic frameworks encountered in numerous pharmaceutically active agents biologically natural products. The catalytic asymmetric Friedel–Crafts reaction of indoles, catalyzed by metal complexes or organocatalysts, is one the most powerful atom-economical approaches to access optically derivatives. Consequently, a wide range electrophilic partners including α,β-unsaturated ketones, esters, amides, imines, β,γ-unsaturated α-keto- α-ketiminoesters, ketimines, nitroalkenes, many others have been successfully employed achieve plethora functionalized moieties. In particular, strategies for C–H functionalization phenyl indoles require incorporation directing blocking group azole ring indole. discovery catalysts which can control enantiodiscrimination has gained great deal attention recent years. This review will provide an updated account on application synthesis diverse derivatives, covering timeframe from 2011 today.

Language: Английский

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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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Asymmetric Construction of Carbon–Fluorine Quaternary Stereogenic Centers via Synergistic Pd/Cu Catalysis

Organic Letters, Journal Year: 2024, Volume and Issue: 26(6), P. 1201 - 1206

Published: Feb. 3, 2024

We developed an asymmetric decarboxylative allylic alkylation of vinylethylene carbonates with α-fluoro pyridinyl acetates through a synergistic palladium/copper catalysis. This protocol provides chiral alcohol carbon–fluorine quaternary stereogenic centers in good yield enantioselectivities and excellent regioselectivities. The utility this approach was further demonstrated via gram-scale experiment derivatizations the product.

Language: Английский

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Covalent Organic Frameworks‐Based Membranes as Promising Modalities from Preparation to Separation Applications: An Overview

The Chemical Record, Journal Year: 2022, Volume and Issue: 22(8)

Published: May 31, 2022

Abstract Covalent organic frameworks (COFs) are a promising class of porous crystalline materials made up covalently connected and periodically protracted network topologies through linkers. The tailorability linker intrinsic structures endow COFs with tunable porosity structure, low density, facilely‐tailored functionality, large surface area, attracting increasing amount interests in variety research areas membrane separations. COF‐based membranes have spawned slew new projects, ranging from fabrication methodologies to separation applications. Herein, we tried emphasis the major developments synthetic approaches based for applications such as, gaseous mixtures, water treatment as well isomeric chiral compounds. proposed methods fabricating continuous columns real world also thoroughly explored. Finally, viewpoint on future directions remaining challenges COF area is provided.

Language: Английский

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Iridium-Catalyzed Asymmetric Cascade Allylation/Retro-Claisen Reaction

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(43), P. 20025 - 20034

Published: Oct. 20, 2022

An enantiomerically enriched 3-hydroxymethyl pentenal unit is one of the key structural cores in plenty natural products and drug candidates with significant biological activities. However, very few synthetic methodologies for facile construction related skeletons have been reported to date. Herein, an elegant iridium-catalyzed asymmetric cascade allylation/retro-Claisen reaction readily available β-diketones VEC was successfully developed, a wide range functionalized chiral derivatives could be prepared good yields excellent enantioselectivities. Various 1,3-diketones ketones containing different electron-withdrawing groups on β-position were well tolerated as outstanding partners high reactivity regio-/chemo-/enantioselectivity. The utility product shown through gram-scale transformation, hydrogenation, cyclopropanation, hydroboration, olefin metathesis. Moreover, this protocol demonstrated applications concise synthesis synthetically useful building block (S)-Taniguchi lactone formal cytisine. A rational pathway proposed based experimental results control experiments.

Language: Английский

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Enantioselective [5 + 1] cycloaddition of sulfur ylides and vinylethylene carbonates via synergistic palladium/chiral phosphonic acid catalysis

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

Published: Jan. 1, 2025

An effective method for the synthesis of dihydropyrans through synergistic palladium and chiral phosphonic acid catalysis was reported. This protocol proceeded under mild reactions provided in up to 87% yield 97% ee.

Language: Английский

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Enantioselective Synthesis of Ten-Membered Lactones via Palladium-Catalyzed [5 + 5] Annulation

Organic Letters, Journal Year: 2023, Volume and Issue: 25(12), P. 2030 - 2035

Published: March 20, 2023

Ten-membered lactones are the core units of many biologically active natural products but with a great synthetic challenge. Based on principle vinylogy, novel types cyclic vinylogous anhydrides have been designed as five-carbon carbonyl synthons, further applied in [5 + 5] annulation vinylethylene carbonates under chiral palladium catalysis. This strategy features excellent regioselectivity, mild conditions, and broad substrate scope, affording range spiro ten-membered bearing oxindole pyrrolidinone motif yield (up to 99%) moderate high enantioselectivity 89% ee).

Language: Английский

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Regio- and stereoselective syntheses of chiral α-quaternary (Z)-trisubstituted allylic amino acidsviasynergistic Pd/Cu catalysis

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(18), P. 2632 - 2635

Published: Jan. 1, 2023

Synergistic palladium/copper catalysis for asymmetric allylic alkylation of vinylethylene carbonates with aldimine esters has been developed the synthesis α-quaternary (Z)-trisubstituted amino acids under mild conditions. This methodology features broad substrate compatibilities in yields up to 87% and 94% ee. A facile scale-up straightforward conversion 1,2,3,5-tetrasubstituted pyrrole 1,2,5,6-tetrahydropyridine bearing chiral quaternary carbon centers verifies synthetic utility this method.

Language: Английский

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Stereodivergent construction of [6.5]-spirocycles bearing three contiguous stereogenic centers by Pd-catalyzed [4+2] annulations

Chem Catalysis, Journal Year: 2023, Volume and Issue: 3(7), P. 100669 - 100669

Published: June 19, 2023

Language: Английский

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Palladium‐ and Iridium‐Catalyzed Deracemization of Allylic Oxygen Compounds with Oxygen Nucleophiles

European Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 2022(44)

Published: Oct. 17, 2022

Abstract Allylic oxygen compounds (AOCs) are an important class of versatile building blocks in natural and non‐natural product synthesis. Catalytic in‐situ deracemization is attractive means for their enantioselective Particularly the AOCs through transition metal‐catalyzed dynamic kinetic asymmetric transformation (DYKAT) with nucleophiles (ONus). This review describes pertinent aspects palladium‐catalyzed DYKAT racemic allylic carboxylates, vinyl oxiranes dioxolanones hydrogen carbonate, alcohols, phenols, oximes, diosphenols water iridium‐catalyzed imidates carboxylates alcohols carboxylic acids. Included discussion desymmetrization meso ‐cycloalkene bis(carboxylates) carbonate. While Trost's bisphosphinobenzamides, Zhou's spiro‐phosphoramidite Feringa's BINOL‐phosphoramidite highly efficient ligands DYKAT, Carreira‐Dorta's BINOL‐phosphoramidite‐olefin excellent ligand DYKAT. also discusses mechanistic structural η 3 ‐allylpalladium‐bisphosphinobenzamide ‐allyliridium‐BINOL‐phosphoramidite‐olefin complexes corresponding catalysts.

Language: Английский

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