Diphenylphosphinite ionic liquid (IL-OPPh2): A solvent and ligand for palladium-catalyzed silylation and dehalogenation reaction of aryl halides with triethylsilane

Iranpoor, Nasser; Firouzabadi, Habib; Azadi, Roya

doi:10.1016/j.jorganchem.2010.01.001

Cited by 55 publications

(14 citation statements)

References 27 publications

(25 reference statements)

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“…However, the participation of base (NMe 3 ) was found to make the silylation process become more exergonic than the reduction process by 6.5 kcal mol −1 . These results agree with the experimental fact that the presence of base is helpful to improve the chemoselectivity for the silylation product …”

Section: Resultssupporting

confidence: 79%

“…Later, based on the silylation of aryl halides with triethylsilane by using an imidazolium‐based phosphinite ionic liquid (IL‐OPPh 2 ) as both solvent and ligand for palladium in the presence of Cs 2 CO 3 as a base, Iranpoor et al. proposed Cycle C as the mechanism . Silylation was supposed to occur through the sequential oxidative addition of triethylsilane and aryl halide to give palladium(IV) species, which was followed by the rapid base‐promoted reductive elimination of HX and subsequent second reductive elimination to generate the silylated product together with the active palladium(0) species to continue the cycle.…”

Section: Introductionmentioning

confidence: 99%

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Mechanistic Insights into Palladium‐Catalyzed Silylation of Aryl Iodides with Hydrosilanes through a DFT Study

Zhang

et al. 2017

Chemistry An Asian Journal

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The catalytic cycles of palladium-catalyzed silylation of aryl iodides, which are initiated by oxidative addition of hydrosilane or aryl iodide through three different mechanisms characterized by intermediates R Si-Pd -H (Cycle A), Ar-Pd -I (Cycle B), and Pd (Cycle C), have been explored in detail by hybrid DFT. Calculations suggest that the chemical selectivity and reactivity of the reaction depend on the ligation state of the catalyst and specific reaction conditions, including feeding order of substrates and the presence of base. For less bulky biligated catalyst, Cycle C is energetically favored over Cycle A, through which the silylation process is slightly favored over the reduction process. Interestingly, for bulky monoligated catalyst, Cycle B is energetically more favored over generally accepted Cycle A, in which the silylation channel is slightly disfavored in comparison to that of the reduction channel. Moreover, the inclusion of base in this channel allows the silylated product become dominant. These findings offer a good explanation for the complex experimental observations. Designing a reaction process that allows the oxidative addition of palladium(0) complex to aryl iodide to occur prior to that with hydrosilane is thus suggested to improve the reactivity and chemoselectivity for the silylated product by encouraging the catalytic cycle to proceed through Cycles B (monoligated Pd catalyst) or C (biligated Pd catalyst), instead of Cycle A.

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Section: Resultssupporting

confidence: 79%

Section: Introductionmentioning

confidence: 99%

Mechanistic Insights into Palladium‐Catalyzed Silylation of Aryl Iodides with Hydrosilanes through a DFT Study

Zhang

et al. 2017

Chemistry An Asian Journal

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“…The tri‐ tert ‐butylphosphine ligand is well known to generate low‐ligated and very reactive palladium species,25–28 which after oxidative addition across the aryl‐iodine bond could undergo transmetallation with the synthesized deuteriosilane. The mechanism below is in line with a recent publication showing that the addition of base to the system results in formation of C–Si silylated products 29…”

Section: Discussionsupporting

confidence: 89%

Homogeneous deuteriodeiodination of iodinated tyrosine in angiotensin‐I using synthesized triethyl[²H]silane and Pd(0)

Pedersen¹,

Martiny²

2010

Labelled Comp Radiopharmac

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“…Based on these findings, in 2010, by using an imidazolium-based phosphinite ionic liquid as both the solvent and ligand for palladium, Iranpoor et al developed a highly efficient catalytic system for the silylation of aryl iodides, bromides and chlorides by using triethylsilane in the presence of cesium carbonate (Cs 2 CO 3 ) (Scheme 47). 57 Other bases including sodium carbonate (Na 2 CO 3 ), sodium acetate (NaOAc) and triethylamine were also effective, but demonstrated slightly lower selectivities and yields. Notably, this catalytic system was even able to convert less active chlorobenzene into triethylsilylbenzene in 89% yield at 120 °C.…”

Section: Short Review Syn Thesis Scheme 46 Palladium-catalyzed Silylamentioning

confidence: 99%

Recent Advances in Transition-Metal-Catalyzed Silylations of Arenes with Hydrosilanes: C–X Bond Cleavage or C–H Bond Activation Synchronized with Si–H Bond Activation

et al. 2015

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Arylsilanes are valuable organosilicon compounds and attract significant research interest due to their promising applications in organic synthesis. The development of aromatic C-Si cross-coupling reactions represents a major challenge in both organosilicon chemistry and organic synthesis. A number of investigations are focused on developing transition-metal-catalyzed Si-C coupling reactions due to the associated high atom economy and superior functional group compatibility. This review describes recent advances in transition-metal-catalyzed selective silylations of aryl C-H and C-X (X = halide) bonds with hydrosilanes.

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Diphenylphosphinite ionic liquid (IL-OPPh2): A solvent and ligand for palladium-catalyzed silylation and dehalogenation reaction of aryl halides with triethylsilane

Cited by 55 publications

References 27 publications

Mechanistic Insights into Palladium‐Catalyzed Silylation of Aryl Iodides with Hydrosilanes through a DFT Study

Mechanistic Insights into Palladium‐Catalyzed Silylation of Aryl Iodides with Hydrosilanes through a DFT Study

Homogeneous deuteriodeiodination of iodinated tyrosine in angiotensin‐I using synthesized triethyl[²H]silane and Pd(0)

Recent Advances in Transition-Metal-Catalyzed Silylations of Arenes with Hydrosilanes: C–X Bond Cleavage or C–H Bond Activation Synchronized with Si–H Bond Activation

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Diphenylphosphinite ionic liquid (IL-OPPh2): A solvent and ligand for palladium-catalyzed silylation and dehalogenation reaction of aryl halides with triethylsilane

Cited by 55 publications

References 27 publications

Mechanistic Insights into Palladium‐Catalyzed Silylation of Aryl Iodides with Hydrosilanes through a DFT Study

Mechanistic Insights into Palladium‐Catalyzed Silylation of Aryl Iodides with Hydrosilanes through a DFT Study

Homogeneous deuteriodeiodination of iodinated tyrosine in angiotensin‐I using synthesized triethyl[2H]silane and Pd(0)

Recent Advances in Transition-Metal-Catalyzed Silylations of Arenes with Hydrosilanes: C–X Bond Cleavage or C–H Bond Activation­ Synchronized with Si–H Bond Activation

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Homogeneous deuteriodeiodination of iodinated tyrosine in angiotensin‐I using synthesized triethyl[²H]silane and Pd(0)

Recent Advances in Transition-Metal-Catalyzed Silylations of Arenes with Hydrosilanes: C–X Bond Cleavage or C–H Bond Activation Synchronized with Si–H Bond Activation