Dienes as Versatile Substrates for Transition Metal‐Catalyzed Reactions

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(20)

Published: March 4, 2024

Abstract Dienes have been of great interest to synthetic chemists as valuable substrates due their abundance and ease synthesis. Their unique stereoelectronic properties enable broad reactivity with a wide range transition metals construct molecular complexity facilitating synthesis biologically active compounds. In addition, structural diene variation can result in substrate‐controlled reactions, providing mechanistic insights into selectivity patterns. The last decade has seen wealth new methodologies involving through the power metal catalysis. This review summarizes recent advances remaining opportunities for metal‐catalyzed transformations dienes.

Language: Английский

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Recent advances in transition metal-catalyzed heteroannulative difunctionalization of alkenes via C–H activation for the synthesis of heterocycles

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(8), P. 2256 - 2279

Published: Jan. 1, 2022

In this review article, we summarized recent advances in the transition metal-catalyzed heteroannulative difunctionalization of alkenes via direct C–H activation to access heterocyclic frameworks.

Language: Английский

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Mapping Ambiphile Reactivity Trends in the Anti‐(Hetero)annulation of Non‐Conjugated Alkenes via Pd^II/Pd^IV Catalysis

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

Published: Jan. 10, 2022

In this study, we systematically evaluate different ambiphilic organohalides for their ability to participate in anti-selective carbo- or heteroannulation with non-conjugated alkenyl amides under Pd

Language: Английский

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Construction of azaheterocycles via Pd-catalyzed migratory cycloannulation reaction of unactivated alkenes

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Aug. 27, 2022

Abstract Azahetereocycles constitute important structural components in many biologically active natural compounds and marketed drugs, represent the most promising scaffolds drug discovery. Accordingly, development of efficient general synthetic methods for construction diverse azaheterocycles is major goal chemistry. Herein, we report a wide range via Pd-catalyzed migratory cycloannulation strategy with unactivated alkenes. This enables rapid synthesis series 6-, 7- 8-membered high efficiency, features broad substrate scope, excellent functional group tolerance under redox-neutral conditions. The significance this finding demonstrated by drug-like molecules step-economy. Preliminary mechanistic investigations reveal that reaction underwent sequentially insertion to alkenes, metal migration process, aza-Michael addition quinone methide intermediate.

Language: Английский

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Transition Metal‐Catalyzed C−H Functionalization Through Electrocatalysis

ChemSusChem, Journal Year: 2023, Volume and Issue: 16(12)

Published: March 7, 2023

Electrochemically promoted transition metal-catalyzed C-H functionalization has emerged as a promising area of research over the last few decades. However, development in this field is still at an early stage compared to traditional reactions using chemical-based oxidizing agents. Recent reports have shown increased attention on electrochemically functionalization. From standpoint sustainability, environmental friendliness, and cost effectiveness, oxidation metal catalyst offers mild, efficient, atom-economical alternative chemical oxidants. This Review discusses advances metal-electrocatalyzed past decade describes how unique features electricity enable economic sustainable way.

Language: Английский

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Palladium(II)-Catalyzed Annulative Difunctionalization of Two Inert C(sp³)–H Bonds by a Bifunctional Reagent

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(11), P. 7627 - 7636

Published: May 22, 2023

Illustrated herein is a Pd(II)-catalyzed direct difunctionalization of two C(sp3)–H bonds aliphatic carboxylic acid derivatives by bifunctional reagents (BFRs) the 2-iodobenzoic series. The methyl 2-pyridyl sulfoximine (MPyS) bidentate directing group (DG), 2-chloro-5-trifluoromethylpyridine ligand, AgOAc as base, and NaBrO3 co-oxidant help concerted metalation deprotonation (CMD) inert bonds, well reductive elimination; density functional theory (DFT) studies shed light on these crucial steps. This process makes [C–C C–O] at gem-α,α′-di-Me groups in single operation, offering access to unusual benzo-fused peripheral-substituted caprolactones. transformation tolerates labile allows construction wide range caprolactones with structural diversity. Mechanistic reveal participation monomeric Pd species catalytic cycle. synthetic versatility complex molecular entities also presented.

Language: Английский

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Recent Advances in Ni‐Catalyzed 1,1‐Difunctionalization of Unactivated Olefins

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 366(4), P. 593 - 602

Published: Dec. 7, 2023

Abstract Unactivated olefins rank amongst the most important feedstocks in organic synthesis. Their availability makes them particularly useful synthons for subsequent functionalization, a catalytic manner. Driven by popularity ascribed nickel catalysis as new tool to rapidly forge molecular architectures via one‐or two‐electron manifolds, recent years have witnessed significant advances Ni‐catalyzed olefin difunctionalization. While 1,2‐difunctionalization or remote functionalization “chain‐walk” become mature disciplines repurposing potential of building blocks, it was only recently that extensions this chemistry 1,1‐difunctionalization been possible. This review summarizes 1,1‐difunctionalization, holding considerable promise powerful strategy our ever‐growing synthetic repertoire.

Language: Английский

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Enantioselective Heck/Tsuji−Trost reaction of flexible vinylic halides with 1,3-dienes

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 22, 2025

Abstract The enantioselective domino Heck/cross-coupling has emerged as a powerful tool in modern chemical synthesis for decades. Despite significant progress relative rigid skeleton substrates, the implementation of asymmetric cascades highly flexible haloalkene substrates remains challenging and long-standing goal. Here we report an efficient Heck/Tsuji−Trost reaction vinylic halides with 1,3-dienes enabled by palladium catalysis. Specifically, Heck insertion stereodetermining step to form ƞ 3 allyl complex situ trapping nucleophiles enable Heck/etherification formal (4 + 2) cycloaddition manner. Engineering Sadphos bearing androgynous non-C 2 -symmetric chiral sulfinamide phosphine ligands are vital component achieving excellent catalytic reactivity enantioselectivity. This strategy offers general, modular divergent platform rapidly upgrading feedstock dienes various value-added molecules is expected inspire development other Heck/cross-couplings.

Language: Английский

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Progress in [4＋1] Cycloadditions of Conjugated Dienes

Chinese Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 45(1), P. 1 - 1

Published: Jan. 1, 2025

Language: Английский

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Construction of aziridine, azetidine, indole and quinoline-like heterocycles via Pd-mediated C–H activation/annulation strategies

Organic & Biomolecular Chemistry, Journal Year: 2021, Volume and Issue: 20(7), P. 1339 - 1359

Published: Dec. 21, 2021

N-Heterocycles can be found in natural products and drug molecules are indispensable components the area of organic synthesis, medicinal chemistry materials science. The construction these N-containing heterocycles by traditional methods usually requires preparation reactive intermediates. In past decades, with rapid growth transition metal catalysed coupling reactions, syntheses from precursors inert chemical bonds have become a challenge. More recently, field associated C-H direct functionalization, efficient been developed for N-heterocyclic compounds such as aziridines, azetidines, indoles quinolines under click type reaction mode. this review, representative synthetic methodologies recent 10 years small class N-heterocycles via Pd-catalysed activation C-N bond formation pathway discussed. We hope article will provide new insights strategies highlighted into future molecular design, synthesis applications medical sciences.

Language: Английский

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