Palladium‐Catalyzed Enantioselective Hydrofunctionalization of Alkenes: Recent Advances

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 26(43)

Published: Sept. 8, 2023

Abstract Palladium‐catalyzed asymmetric hydrofunctionalization of alkenes is one the most powerful and straightforward methods to forge a new C−H bond C−X (X=C, N, O, F, Si etc) bond, which provides an efficient way obtain valuable enantioenriched molecules from cheap readily available feedstocks. Catalytic simple challenging but still highly sought after. This review will mainly focus on recent advances in Palladium catalyzed over past decade, including hydroamination, hydrooxygenation, hydrofluorination, hydrosilylation, hydroarylation, hydroalkenylation hydrocarbonylation.

Language: Английский

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

Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(5), P. 1474 - 1481

Published: April 17, 2023

Language: Английский

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Enantioconvergent synthesis of axially chiral amides enabled by Pd-catalyzed dynamic kinetic asymmetric aminocarbonylation

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Aug. 23, 2024

Atropisomeric biaryls bearing carbonyl groups have attracted increasing attention due to their prevalence in diverse bioactive molecules and crucial role as efficient organo-catalysts or ligands asymmetric transformations. However, preparation often involves tedious multiple steps, the direct synthesis via carbonylation has scarcely been investigated. Herein, we report an palladium-catalyzed enantioconvergent aminocarbonylation of racemic heterobiaryl triflates with amines dynamic kinetic transformation (DyKAT). This protocol features a broad substrate scope excellent compatibility for rapid construction axially chiral amides good high yields enantioselectivities. Detailed mechanistic investigations discover that base can impede intramolecular hydrogen bond-assisted axis rotation products, thus allowing success achieve enantioselectivity. Moreover, achieved be directly utilized N,N,N-pincer copper-catalyzed enantioselective formation C(sp3)-N C(sp3)-P bonds. Axially containing not only exist various drug candidates but also serve authors transformation.

Language: Английский

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

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8739 - 8747

Published: May 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.

Language: Английский

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Palladium-catalyzed tandem Heck/carbonylation/aminocarbonylation en route to chiral heterocyclic α-ketoamides

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 9(4), P. 939 - 945

Published: Dec. 23, 2021

An unprecedented tandem carbonylation/aminocarbonylation triggered by palladium-catalyzed enantioselective Heck-type exocyclopalladation delivering chiral heterocyclic α-ketoamides has been developed.

Language: Английский

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Pd‐Catalyzed Asymmetric 5‐exo‐trig Cyclization/Cyclopropanation/Carbonylation of 1,6‐Enynes for the Construction of Chiral 3‐Azabicyclo[3.1.0]hexanes

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(4)

Published: Nov. 25, 2022

We herein disclose a mild and efficient access to chiral 3-azabicyclo[3.1.0]hexanes via Pd-catalyzed asymmetric 5-exo-trig cyclization/cyclopropanation/carbonylation of 1,6-enynes. Various nucleophiles, such as alcohols, phenols, amines water, are well compatible with the reaction system. This forms three C-C bonds, two rings, adjacent quaternary carbon stereocenters one C-O/C-N bond excellent regio- enantioselectivities. The products could be further functionalized generate library 3-azabicyclo[3.1.0]hexane frameworks.

Language: Английский

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Carbonylative Transformations Using a DMAP-Based Pd-Catalyst through Ex Situ CO Generation

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(21), P. 15218 - 15236

Published: Oct. 24, 2023

A phosphine-free, efficient protocol for aminocarbonylation and carbonylative Suzuki-Miyaura coupling has been developed using a novel palladium complex, [PdII(DMAP)2(OAc)2]. The complex was successfully synthesized stoichiometric reaction between PdII(OAc)2 DMAP in acetone at room temperature characterized single-crystal X-ray analysis. Only 5 mol % catalyst loading sufficient effective transformations. "Chloroform-COware" chemistry utilized safe facile insertion of the carbonyl unit chloroform as an inexpensive CO source two-chamber setup. Various value-added pharmaceutically relevant compounds such CX-516, CX-546, farampator were technique. Furthermore, commercially designed COware engineered to COware-RB setup sequential one-pot synthesis indenoisoquinolines (topoisomerase I inhibitors).

Language: Английский

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Palladium-Catalyzed Dual C–H Carbonylation of Diarylamines Leading to Diversified Acridones under CO-Free Conditions

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(3), P. 2014 - 2023

Published: Jan. 19, 2024

A Pd-catalyzed dual C-H carbonylation of commercially available diarylamines using Co

Language: Английский

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Palladium-Catalyzed Three-Component Cascade Carbonylation Reaction to Construct Benzofuran Derivatives

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(11), P. 7741 - 7746

Published: May 14, 2024

A novel three-component cyclization carbonylation reaction of iodoarene-tethered propargyl ethers with amine and CO is reported. This palladium-catalyzed cascade undergoes a sequence oxidative addition, unsaturated bond migration, carbonyl insertion, nucleophilic attack to deliver the benzofuran skeleton. Both aromatic amines aliphatic could proceed smoothly in this transformation under one atm CO.

Language: Английский

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Umpolung‐Enabled Divergent Dearomative Carbonylations

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(33)

Published: May 31, 2024

Although dearomative functionalizations enable the direct conversion of flat aromatics into precious three-dimensional architectures, case for simple arenes remains largely underdeveloped owing to high aromatic stabilization energy. We herein report a sequential addition two nucleophiles arene π-bonds through umpolung chromium-arene complexes. This mode enables divergent carbonylation reactions benzene derivatives by tolerating various in combination with alcohols or amines under CO-gas-free conditions, thus providing modular access functionalized esters amides. The tunable synthesis 1,3- 1,4-cyclohexadienes as well construction carbon quaternary centers further highlight versatility this dearomatization. Diverse late-stage modifications and derivatizations towards synthetically challenging bioactive molecules reveal synthetic utility. A possible mechanism was proposed based on control experiments intermediate tracking.

Language: Английский

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