Mechanistic pathways for oxidative addition of aryl iodides to the low-ligated diethanolamine palladium(0) complex in phosphine-free Heck reactions

Petrović, Zorica D.; Petrović, Vladimir P.; Simijonović, Dušica; Marković, Svetlana

doi:10.1016/j.jorganchem.2009.07.043

Cited by 20 publications

(8 citation statements)

References 39 publications

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“…One of the most important stages of the catalytic cycle in these reactions is the oxidative addition of an aryl halide, during which the metal center acts as a nucleophile (that is, as a Lewis base). According to the assumption of some researchers, confirmed by theoretical calculations, , the Ph–I···Pd coordinative XB was formed in the intermediate. Besides, it was also shown that the I–I···Pd coordinative XB may be formed in one of the intermediates in the Pd II -catalyzed C–H iodination with molecular iodine.…”

Section: Introductionmentioning

confidence: 83%

“…One of the most important stages of the catalytic cycle in these reactions is the oxidative addition of an aryl halide, during which the metal center acts as a nucleophile (that is, as a Lewis base). According to the assumption of some researchers, confirmed by theoretical calculations, 23,24 molecular iodine. Therefore, an experimental confirmation of the possibility of such contacts would be very useful also for studying the mechanism of these catalytic reactions.…”

Section: ■ Introductionmentioning

confidence: 87%

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Pt/Pd and I/Br Isostructural Exchange Provides Formation of C–I···Pd, C–Br···Pt, and C–Br···Pd Metal-Involving Halogen Bonding

Baykov

Dabranskaya

Ivanov

et al. 2018

Crystal Growth & Design

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Complexes trans-[MCl2(NCNMe2)2] (M = Pt 1, Pd 2) were cocrystallized with CHBr3 and CHI3, forming 1:2 adducts isomorphic with previously reported trans-[PtCl2(NCNMe2)2]·2CHI3. In all cases, the C–X···M (X = Br, I; M = Pd, Pt) metal-involving halogen bonding together with numerous chloride-halomethane halogen and hydrogen bonds were identified by single-crystal XRD experiments. Further DFT calculations and topological analysis of the electron density distribution within the framework of QTAIM method at the M06/DZP-DKH level of theory confirmed the existence of these interactions and their noncovalent nature. Estimated energies of such contacts vary from 1.6 to 3.1 kcal/mol.

show abstract

Section: Introductionmentioning

confidence: 83%

“…One of the most important stages of the catalytic cycle in these reactions is the oxidative addition of an aryl halide, during which the metal center acts as a nucleophile (that is, as a Lewis base). According to the assumption of some researchers, confirmed by theoretical calculations, 23,24 molecular iodine. Therefore, an experimental confirmation of the possibility of such contacts would be very useful also for studying the mechanism of these catalytic reactions.…”

Section: ■ Introductionmentioning

confidence: 87%

Pt/Pd and I/Br Isostructural Exchange Provides Formation of C–I···Pd, C–Br···Pt, and C–Br···Pd Metal-Involving Halogen Bonding

Baykov

Dabranskaya

Ivanov

et al. 2018

Crystal Growth & Design

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“…The main steps of the Pd-mediated Heck reaction are oxidative addition, alkene insertion, and reductive elimination. The oxidative addition of aryl halides to Pd complexes to form aryl-palladium species is the first step in the Heck reaction (shown in Scheme ), which is usually the rate-determining step of this reaction. − Aryl bromides, iodides, and chlorides are the general substrates used in this category. Chlorides are generally more cost-effective; however, they are more unreactive, and efforts have been made to render them more reactive. , Thus, the oxidative addition of chlorobenzene onto Pd/CBNTs was chosen to test the catalytic activities of the single Pd atom catalysts (Figure ).…”

Section: Resultsmentioning

confidence: 99%

Computational Study of Carbon-Doped Boron Nitride Nanotubes Loaded with Pd Atoms as Single-Atom Catalysts for Heck Reactions

Cao

Wang

Ran

et al. 2020

ACS Appl. Nano Mater.

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Heterogeneous single-atom catalysts (SACs) involve isolated metal atoms anchored to a support, displaying high catalytic activity and stability in many chemical reactions. This work reports a computational study of six carbon atom-doped (8, 0) single-walled boron nitride nanotubes (CBNTs) loading Pd atom as SACs for Heck reaction. The coordinative structure−catalytic performance relationship of the Pd1/CBNT SACs was investigated. Our simulations demonstrate that the activity of the Pd1/CBNT catalysts depends on the coordination number between the Pd center and the support as well as the local electronic environment around the Pd atom. Moreover, the difference between the Pd−C (carbon atom in a carrier) and Pd−C Ph (carbon atom in chlorobenzene) bond orders could be used as a descriptor of the activity of the SACs. The Pd1/BNT-CN (the nitrogen atom of BNT was replaced with carbon atom) catalyst was found to be optimum for the Heck reaction, owing to its excellent stability and activity that was even higher than their homogeneous analogues. Thus, this study provides a method for the design and screening of SACs for both high stability and activity of the Heck reaction.

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“…A byproduct from the boronic ester hydrolysis is diethanolamine (Scheme ), and we questioned whether this could affect the catalysis. Palladium–diethanolamine complexes are known, and diethanolamine-based solid-supported scavengers have been developed for metal removal. , It was therefore conceivable that diethanolamine was inhibiting the catalysis through the potentially reversible formation of a non-productive palladium–diethanolamine complex.…”

Section: Resultsmentioning

confidence: 99%

Process Development of a Suzuki Reaction Used in the Manufacture of Lanabecestat

Ashworth

Campbell

Cherryman

et al. 2018

Org. Process Res. Dev.

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We developed a scalable Suzuki process for the synthesis of lanabecestat (+)-camsylate, an active pharmaceutical ingredient that was recently investigated in a Phase III clinical program for the treatment of early Alzheimer's disease. The evolution of this process culminated with the use of a stable and crystalline diethanolamine boronic ester that rapidly hydrolyses under the reaction conditions. Herein, we report that the liberated diethanolamine plays an important role in the catalytic process, with supporting evidence for an equilibrium between an unbound and bound palladium complex. Additionally, the diethanolamine acts as an internal scavenger during the crystallization of lanabecestat by increasing the solubility of the palladium species, obviating the need for a discrete scavenging step.

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Mechanistic pathways for oxidative addition of aryl iodides to the low-ligated diethanolamine palladium(0) complex in phosphine-free Heck reactions

Cited by 20 publications

References 39 publications

Pt/Pd and I/Br Isostructural Exchange Provides Formation of C–I···Pd, C–Br···Pt, and C–Br···Pd Metal-Involving Halogen Bonding

Pt/Pd and I/Br Isostructural Exchange Provides Formation of C–I···Pd, C–Br···Pt, and C–Br···Pd Metal-Involving Halogen Bonding

Computational Study of Carbon-Doped Boron Nitride Nanotubes Loaded with Pd Atoms as Single-Atom Catalysts for Heck Reactions

Process Development of a Suzuki Reaction Used in the Manufacture of Lanabecestat

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