The Sonogashira Reaction

Chinchílla, Rafael; Nájera, Carmén

doi:10.1002/9783527677894.ch10

Cited by 3 publications

(1 citation statement)

References 213 publications

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“…The Suzuki–Miyaura cross-coupling reaction is the most explored, followed by the Heck and the Heck–Cassar–Sonogashira (HCS) reactions. In particular, the last ones consist of the palladium-catalyzed substitution of a terminal alkyne hydrogen with an aromatic ring (Scheme ), and several applications in the pharma industry have been reported …”

Section: Introductionmentioning

confidence: 99%

New Mechanistic Insights into the Copper-Free Heck–Cassar–Sonogashira Cross-Coupling Reaction

Palladino,

Fantoni,

Ferrazzano

et al. 2023

ACS Catal.

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The copper-free Heck–Cassar–Sonogashira (HCS) reaction, known since 1975, nowadays represents one of the most powerful methods for C–C bond formation in organic synthesis with several industrial applications. Despite its great success, the mechanism is still under discussion, with several reported possible pathways. To clarify the copper-free HCS reaction mechanism, stoichiometric and catalytic reactions were carried out and monitored by 31P/1H NMR spectroscopy, HPLC, and GC chromatography. In particular, the investigation of the role of the base, mimicking the real catalytic conditions, highlighted the fact that secondary amines rapidly induce precatalyst reduction and decrease the energy barrier for the alkyne carbopalladation step. The results supported the mechanism via direct coordination of the terminal alkyne on the oxidative addition complex. Depending on the palladium counterion, and independent of the solvent, aromatic substitutions, temperature, and terminal alkyne substitution, these studies support two different pathways: with halides, a neutral route, and with the triflate, a cationic one.

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Section: Introductionmentioning

confidence: 99%

New Mechanistic Insights into the Copper-Free Heck–Cassar–Sonogashira Cross-Coupling Reaction

Palladino,

Fantoni,

Ferrazzano

et al. 2023

ACS Catal.

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Synthesis, structural properties and reactivity of ruthenocene-based pincer Pd(ii) tetrahydroborate

et al. 2019

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1.2.4 Gold/Photocatalyst Dual Catalysis

Barriault¹,

Zidan²,

Rohe³

2020

Dual Catalysis in Organic Synthesis 1

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The use of gold catalysts in classical two-electron cross-couplings is notoriously impractical due to the high oxidation potential of gold(I)/gold(III) [e.g., E0 (AuI/AuIII) = +1.36 V]. However, when used in tandem with photocatalysts, the gold center can be oxidized one electron at a time, making cross-coupling style reactions with gold more viable. The gold(III) intermediate also has the potential to act as a Lewis acid prior to its reductive elimination step, which has spurred development of multi-bond-forming dual catalytic transformations. This dual-catalytic strategy is also applied in reactions with gold as a photocatalyst in conjunction with an organocatalyst to effectuate traditionally challenging cross couplings.

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The Sonogashira Reaction

Cited by 3 publications

References 213 publications

New Mechanistic Insights into the Copper-Free Heck–Cassar–Sonogashira Cross-Coupling Reaction

New Mechanistic Insights into the Copper-Free Heck–Cassar–Sonogashira Cross-Coupling Reaction

Synthesis, structural properties and reactivity of ruthenocene-based pincer Pd(ii) tetrahydroborate

1.2.4 Gold/Photocatalyst Dual Catalysis

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