Designing Homogeneous Copper-Free Sonogashira Reaction through a Prism of Pd–Pd Transmetalation

Martek, Bruno Aleksander; Gazvoda, Martin; Urankar, Damijana; Košmrlj, Janez

doi:10.1021/acs.orglett.0c01227

Cited by 25 publications

(9 citation statements)

References 57 publications

(52 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Recently, however, Kosmrlj and co-workers disclosed an intriguing "copper-free" variant of the Sonogashira reaction that made use of two distinct palladium catalysts to fulfill the traditional role of Pd (to activate the aryl halide 373) and Cu (to activate the acetylene 374). 186 In this fully synergistic, Pd/Pd catalysis, cross-coupled product 375 are furnished in good yields (Scheme 52).…”

Section: "Copper-free" Sonogashira Reaction Via Synergistic Pd/pd Cat...mentioning

confidence: 99%

Synergistic Dual Transition Metal Catalysis

et al. 2020

View full text Add to dashboard Cite

Synergistic catalysis, a type of plural catalysis which utilizes at least two different catalysts to enable a reaction between two separately activated substrates, has unlocked a plethora of previously unattainable transformations and novel chemical reactivity. Despite the appreciable utility of synergistic catalysis, specific examples involving two transition metals have been limited, as ensuring a judicious choice of reaction parameters to prevent deactivation of catalysts, undesirable monocatalytic event(s) leading to side products, or premature termination and other potentially troublesome outcomes present a formidable challenge. Excluding those driven by photocatalytic mechanisms, this review will highlight the reported examples of reactions that make use of two simultaneous catalytic cycles driven by two transition metal catalysts.

show abstract

Section: "Copper-free" Sonogashira Reaction Via Synergistic Pd/pd Cat...mentioning

confidence: 99%

Synergistic Dual Transition Metal Catalysis

et al. 2020

View full text Add to dashboard Cite

show abstract

“…Sonogashira coupling is one of the most useful methods for the construction of conjugated aromatic alkynes which are crude precursors for various natural products, [54–55] drugs [56] and functional materials [57–58] . Recently, the catalytic Sonogashira couplings in the absence of copper salts are becoming more and more popular due to the toxic side effects of copper additives [59–61] …”

Section: Resultsmentioning

confidence: 99%

“…[57][58] Recently, the catalytic Sonogashira couplings in the absence of copper salts are becoming more and more popular due to the toxic side effects of copper additives. [59][60][61]…”

Section: Sonogashira Reactionmentioning

confidence: 99%

C−I Selective Sonogashira and Heck Coupling Reactions Catalyzed by Aromatic Triangular Tri‐palladium

et al. 2022

View full text Add to dashboard Cite

Aromatic triangular tri‐palladium cations 1–3, abbreviated as [Pd3]+, have shown interesting photoelectric properties, Lewis basic character, and excellent activities in catalytic hydrogenation. Herein, we report the highly efficient and C−I selective Sonogashira and Heck coupling reactions catalyzed by these tri‐palladium complexes. Benefiting from the moderate C−I bond association energy, these tri‐palladiums presented exclusive reactivities to aryl iodides over the brominated aromatics in coupling reactions. In the Sonogashira pathway, good to excellent isolated yields (71–95 %) were achieved. Gram‐scale reaction reached 93 % of yield with palladium loading as few as 0.06 mol %. We also explored the electronic and steric effects for phenyl alkynes and aryl iodides including heteroaromatics like thiophene, pyridine, pyrazole, and pyrazine. Similarly, yields of 71–96 % were obtained for palladium loading of 1.5 mol% through catalyzed Heck coupling of aryl iodides and alkenes. The HRMS monitoring revealed that [Pd3]+ maintained as whole entity during the catalytic process due to its robusness.

show abstract

“…Sonogashira cross-coupling is a widely useful synthetic tool allowing the introduction of an acetylenic moiety in a variety of molecular structures. − Since the seminal work by Sonogashira and Hagihara, the protocol has been largely studied and improved by exploiting the use of inorganic or organic bases under homogeneous or heterogeneous conditions and in the presence of a wide range of reaction media. − …”

Section: Introductionmentioning

confidence: 99%

Biomass Waste-Derived Pd–PiNe Catalyst for the Continuous-Flow Copper-Free Sonogashira Reaction in a CPME–Water Azeotropic Mixture

Ferlin

Valentini

Sciosci

et al. 2021

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

Herein, we report on the development of a waste minimization/valorization methodology applied to the representative benchmark Sonogashira cross-coupling reaction performed in a continuous-flow reactor, featuring a continuous-flow downstream membrane organic/aqueous separator to recover medium and products with minimal waste. The protocol is based on the use of a biomass waste-derived heterogeneous Pd-based catalyst, which is obtained from the valorization of urban-waste pine needles (PiNe). In a circular economy approach, the PiNe biomass has been proven to be capable of producing an effective active carbon support for Pd nanoparticle immobilization. In addition, the catalyst has been utilized in an azeotropic mixture formed by industrial wastederived cyclopentyl methyl ether (CPME) and water. Thanks to this combination and with the adoption of flow conditions, high yields of final target products could be accessed with high stability and durability of the catalyst. Final isolation of the products has been realized by setting an in-line liquid−liquid separator in flow, which has also allowed CPME recovery with a significant reduction of the waste generated. The protocol has been applied to the representative preparation of eniluracil, a GSK API.

show abstract

Designing Homogeneous Copper-Free Sonogashira Reaction through a Prism of Pd–Pd Transmetalation

Cited by 25 publications

References 57 publications

Synergistic Dual Transition Metal Catalysis

Synergistic Dual Transition Metal Catalysis

C−I Selective Sonogashira and Heck Coupling Reactions Catalyzed by Aromatic Triangular Tri‐palladium

Biomass Waste-Derived Pd–PiNe Catalyst for the Continuous-Flow Copper-Free Sonogashira Reaction in a CPME–Water Azeotropic Mixture

Contact Info

Product

Resources

About