Palladium-Catalyzed Heck-Type Coupling of Allyl Esters: β-Hydride versus β-Acetoxy Elimination

Pan, Delin; Jiao, Ning

doi:10.1055/s-0030-1258083

Cited by 7 publications

(1 citation statement)

References 23 publications

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“…Allylic esters are commonly used as allylation reagents in organic synthesis. − Jiao et al, White et al, and Xiao et al reported oxidative Heck reactions of allylic esters with arylboronic acids, which occurred via β-hydride elimination rather than β-OAc elimination. In 2011, Liu et al reported olefination of (poly)fluoroarenes with allyl esters via an oxidative coupling process using [Pd(OAc) 2 ] as the catalyst and AgOAc as the base and the oxidant.…”

Section: C-c Bond Forming Reactionsmentioning

confidence: 99%

Applications of Transition Metal-Catalyzed ortho-Fluorine-Directed C–H Functionalization of (Poly)fluoroarenes in Organic Synthesis

Budiman,

Perutz,

Steel

et al. 2024

Chem. Rev.

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The synthesis of organic compounds efficiently via fewer steps but in higher yields is desirable as this reduces energy and reagent use, waste production, and thus environmental impact as well as cost. The reactivity of C−H bonds ortho to fluorine substituents in (poly)fluoroarenes with metal centers is enhanced relative to meta and para positions. Thus, direct C−H functionalization of (poly)fluoroarenes without prefunctionalization is becoming a significant area of research in organic chemistry. Novel and selective methodologies to functionalize (poly)fluorinated arenes by taking advantage of the reactivity of C−H bonds ortho to C−F bonds are continuously being developed. This review summarizes the reasons for the enhanced reactivity and the consequent developments in the synthesis of valuable (poly)fluoroarene-containing organic compounds.

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Section: C-c Bond Forming Reactionsmentioning

confidence: 99%

Applications of Transition Metal-Catalyzed ortho-Fluorine-Directed C–H Functionalization of (Poly)fluoroarenes in Organic Synthesis

Budiman,

Perutz,

Steel

et al. 2024

Chem. Rev.

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Formation of Alkenes by Metal‐promoted Coupling Reactions

Larock

Zeni

2018

Comprehensive Organic Transformations

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Alkali Metal Reagents Grignard Reagents Boron Reagents Aluminum Reagents Indium Reagents Thallium Reagents Silicon Reagents Germanium Reagents Tin Reagents Bismuth Reagents Arsenic Reagents Sulfur Reagents Selenium Reagents Tellurium Reagents Titanium Reagents Zirconium Reagents Vanadium Reagents Molybdenum Reagents Manganese Reagents Iron Reagents Ruthenium Reagents Cobalt Reagents Nickel Reagents Palladium Reagents Copper Reagents Silver Reagents Zinc Reagents Mercury Reagents Olefin Metathesis

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An Explicit Interpretation of the Directing Group Effect for the Pd(OAc)₂-Catalyzed Aromatic C–H Activations

Zhang

Fang

2016

J. Org. Chem.

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A comprehensive DFT investigation has been performed for a series of the Pd(OAc)2-catalyzed C-H activations, updating and extending the understanding of directing group effect. In the beginning, the directed and undirected C-H activation mechanisms, based on 10 model reactions, have been discussed comparatively, which disclosed that directing group can exert a thermodynamic driving force, not necessarily a kinetic promotion, on the C-H activation process. Formation of the open palladation species via the undirected pathway is thermodynamically unspontaneous (ΔG = 4-9 kcal/mol), in sharp contrast to that of the cyclopalladation species via the directed pathway (ΔG < 0). Further calculations revealed that the free-energy barriers of proton-transfer are in fact not so high on the undirected pathway (17-24 kcal/mol), while mediation of some O-center groups in the directed pathway would increase the free-energy barriers of proton-transfer. For pyridine N-oxide systems, the undirected mechanism was estimated to be more plausible than the 4-member-directed one both thermodynamically and kinetically. In addition, the uncommon 7-membered cyclopalladation has been tentatively explored using two current examples, predicting that electron-rich directing groups can help to stabilize the 7-membered palladacycles formed.

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Palladium-Catalyzed Heck-Type Coupling of Allyl Esters: β-Hydride versus β-Acetoxy Elimination

Abstract: This account presents recent progress in palladiumcatalyzed Heck-type reactions of allyl esters with aryl halides, arylmetallic reagents, or arenes. Many improvements have been achieved to control the regioselectivity of b-hydride or b-acetoxy elimination.

Cited by 7 publications

References 23 publications

Applications of Transition Metal-Catalyzed ortho-Fluorine-Directed C–H Functionalization of (Poly)fluoroarenes in Organic Synthesis

Applications of Transition Metal-Catalyzed ortho-Fluorine-Directed C–H Functionalization of (Poly)fluoroarenes in Organic Synthesis

Formation of Alkenes by Metal‐promoted Coupling Reactions

An Explicit Interpretation of the Directing Group Effect for the Pd(OAc)₂-Catalyzed Aromatic C–H Activations

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Palladium-Catalyzed Heck-Type Coupling of Allyl Esters: β-Hydride versus β-Acetoxy Elimination

Abstract: This account presents recent progress in palladiumcatalyzed Heck-type reactions of allyl esters with aryl halides, arylmetallic reagents, or arenes. Many improvements have been achieved to control the regioselectivity of b-hydride or b-acetoxy elimination.

Cited by 7 publications

References 23 publications

Applications of Transition Metal-Catalyzed ortho-Fluorine-Directed C–H Functionalization of (Poly)fluoroarenes in Organic Synthesis

Applications of Transition Metal-Catalyzed ortho-Fluorine-Directed C–H Functionalization of (Poly)fluoroarenes in Organic Synthesis

Formation of Alkenes by Metal‐promoted Coupling Reactions

An Explicit Interpretation of the Directing Group Effect for the Pd(OAc)2-Catalyzed Aromatic C–H Activations

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An Explicit Interpretation of the Directing Group Effect for the Pd(OAc)₂-Catalyzed Aromatic C–H Activations