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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Palladium-Catalyzed Asymmetric Dearomative Carbonylation of Indoles

Organic Letters, Journal Year: 2022, Volume and Issue: 24(16), P. 3033 - 3037

Published: April 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.

Language: Английский

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Recent Developments in Enantioselective Domino Reactions. Part A: Noble Metal Catalysts

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(5), P. 620 - 681

Published: Jan. 17, 2023

Abstract This review updates the field of enantioselective domino reactions promoted by chiral catalysts derived from noble metals, including palladium, silver, rhodium, ruthenium, iridium and gold, published since beginning 2019. It illustrates how much a diversity these allow unprecedented asymmetric many types to be achieved with excellent enantioselectivity, giving direct access wide variety complex molecules. magnified image

Language: Английский

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Transition‐Metal‐Catalyzed Transformations Involving the Heck Reaction

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(15), P. 2436 - 2466

Published: June 12, 2023

Abstract Elaborated molecular architectures including complex carbocycles, heterocycles, and polycyclic structures represent an important class of organic compounds because they are ubiquitous structural units in a broad variety biologically pharmacologically relevant natural products, medicinal molecules, functional materials. A major challenge modern synthetic methodology is the development strategically efficient selective construction these from readily available starting Transition‐metal‐catalyzed transformations involving Heck reaction as pivotal step have afforded powerful approach for accessing sophisticated skeletons set easy‐to handle materials, thus highlighting its potential significance streamlining drug discovery process. Over past few decades, significant effort has been devoted to derivatives versatile routes, number direct strategies reported. In this review, latest advances transition‐metal‐catalyzed critical summarized, which could be divided into six categories: 1) Heck/Sonogashira tandem reaction; 2) Heck/Suzuki 3) Heck/Heck 4) Heck/Hiyama 5) Heck/Cacchi 6) Heck/C−H bond functionalization reaction.

Language: Английский

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Diastereo- and Enantioselective Dearomative Reductive Aryl-Fluoroalkenylation of Indoles by Nickel Catalysis

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(9), P. 6432 - 6439

Published: April 11, 2024

Herein, we disclose a nickel-catalyzed dearomative reductive aryl-fluoroalkenylation of indoles by defluorinative coupling with gem-difluoroalkenes. The catalytic protocol affords facile assembly various monofluoroalkene-containing polycyclic fused indolines bearing two contiguous carbon stereocenters in high diastereo- and enantioselectivities tolerance diverse functional groups.

Language: Английский

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Enantioselective Pd-catalyzed dearomative reductive Heck and domino Heck–Suzuki reactions of 2-CF₃-indoles

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(42), P. 6200 - 6203

Published: Jan. 1, 2022

Highly enantioselective palladium-catalyzed dearomative reductive Heck reaction and domino Heck-Suzuki of 2-CF3-indoles have been developed. Using Pd(OAc)2/(R)-Synphos as the catalyst Et3SiH a hydride source, variety indolines bearing 2-trifluoromethyl quaternary stereocenter were obtained via reaction. Alternatively, using Pd(dba)2/phosphoramidite Ar4BNa coupling partner, structurally diverse containing two vicinal carbon stereocenters afforded through

Language: Английский

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Recent Advances in the Synthesis of Indolines via Dearomative Annulation of N‐acylindoles

Asian Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 11(10)

Published: Aug. 3, 2022

Abstract Polycyclic fused indoline derivatives, specifically those bearing tertiary or quaternary carbon stereocenters at C2 and C3 positions, stand as an important class of nitrogen‐containing heterocyclic compounds because they are frequently occurring core structures in a wide variety alkaloid natural products, pharmaceutical molecules, functional materials. Over the past few decades, development new versatile synthetic approaches for construction indolines has been focus great deal research initiatives. In this review, recent advances dearomative annulation N‐ acylindoles with diverse nucleophiles summarized since 2012, which could be divided into five categories: 1) Dearomative Heck reactions acylindoles; 2) Visible‐light‐induced reductive dearomatization 3) Lewis acid‐catalyzed 4) Asymmetric 5) by other closely related reagents.

Language: Английский

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Pd-Catalyzed Asymmetric Dearomative Arylation of Indoles via a Desymmetrization Strategy

Organic Letters, Journal Year: 2022, Volume and Issue: 24(7), P. 1481 - 1485

Published: Feb. 14, 2022

Pd-catalyzed asymmetric dearomative arylation of C3-substituted indoles is realized via a desymmetrization strategy. A BINOL-derived chiral phosphoramidite ligand found to be highly efficient for the stereoselective control in this reaction. This method provides convenient synthesis spiroindolenines bearing two stereogenic centers good yields (up 98%) with excellent diastereo- and enantioselectivities >20:1 dr 97% ee), which could also applied simple C3-tethered indoles.

Language: Английский

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Divergent Synthesis of Indolenine and Indoline Ring Systems by Palladium‐Catalyzed Asymmetric Dearomatization of Indoles**

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(13)

Published: Jan. 26, 2022

Abstract Dearomatized indole derivatives bearing a C3‐ or C2‐stereocenter exist ubiquitously in natural products and biologically active molecules. Despite remarkable advances their synthesis, stereoselective regio‐divergent methods are still high demand. Herein, Pd‐catalyzed intermolecular asymmetric spiroannulation of 2,3‐disubstituted indoles with internal alkynes has been developed for the efficient construction indoline structures C2‐quaternary stereocenter. Stereospecific aza‐semipinacol rearrangement these under acidic conditions afforded indolenine C3‐quaternary stereocenter, where migrating group could be controlled by reaction sequence. The together subsequent enabled divergent access to dearomatized either

Language: Английский

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Nickel-Catalyzed Enantioselective Dearomative Heck-Reductive Allylic Defluorination Reaction of Indoles

Organic Letters, Journal Year: 2023, Volume and Issue: 25(33), P. 6122 - 6127

Published: Aug. 14, 2023

Herein, we describe a nickel-catalyzed asymmetric dearomative aryl-difluoroallylation reaction of indoles with α-trifluoromethyl alkenes as an electrophilic coupling partner. The proceeds via cascade sequence involving Heck cyclization and reductive allylic defluorination. A series gem-difluoroallyl substituted indolines are obtained in moderate to good yields (36-77% yield) excellent enantioselectivity (up 99% ee). features broad functional group tolerance, scaled-up synthesis, late-stage diversification.

Language: Английский

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