Halide and pseudohalide effects in Pd-catalysed cross-coupling reactions

Fairlamb, Ian J. S.; Taylor, Richard J.K.; Serrano, José Luís; Sánchez, Gregorio

doi:10.1039/b605699g

Cited by 63 publications

(33 citation statements)

References 80 publications

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“…It has been reported that the reaction rate is not first order with respect to the concentration of the catalyst when NPs are the true catalytic species. [42,[45][46][47][48][49] Therefore, these data further supported the conclusion that 1 was homogenous rather than heterogeneous in this catalytic system.…”

Section: Resultssupporting

confidence: 72%

Identification of a Highly Efficient Alkylated Pincer Thioimido–Palladium(II) Complex as the Active Catalyst in Negishi Coupling

Liu

Wang

Zhang

et al. 2009

Chemistry A European J

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The induction period of Negishi coupling catalyzed by pincer thioamide-palladium complex 1 was investigated. A heterogeneous mechanism was excluded by kinetic studies and comparison with Negishi coupling reactions promoted by Pd(OAc)(2)/Bu(4)NBr (a palladium-nanoparticle system). Tetramer 2 was isolated from the reaction of 1 and organozinc reagents. Dissociation of complex 2 by PPh(3) was achieved, and the structure of resultant complex 8 was confirmed by X-ray diffraction analysis. A novel alkylated pincer thioimido-Pd(II) complex, 7, generated from catalyst precursor 1 and basic organometallic reagents (RM), was observed by in situ IR, (1)H NMR, and (13)C NMR spectroscopy for the first time. The reaction of 7 with methyl 2-iodobenzoate afforded 74% of the cross-coupled product, methyl 2-methylbenzoate, together with 60% of Pd(II) complex 2. Furthermore, the catalyst, as an electron-rich Pd(II) species, efficiently promoted the Negishi coupling of aryl iodides and alkylzinc reagents without an induction period, even at low temperatures (0 degrees C or -20 degrees C). To evaluate the influence of the catalyst structure upon the induction period, complex 9 was prepared, in which the nBu groups of 1 were displaced by more bulky 1,3,5-trimethylphenyl groups. Trimer 10 was isolated from the reaction of complex 9 and basic organometallic reagents such as CyZnCl or CyMgCl (Cy: cyclohexyl); this is consistent with the result obtained with complex 1. The rate in the induction period of the model reaction catalyzed by 9 was faster than that with 1. Plausible catalytic cycles for the reaction, based upon the experimental results, are discussed.

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Section: Resultssupporting

confidence: 72%

Identification of a Highly Efficient Alkylated Pincer Thioimido–Palladium(II) Complex as the Active Catalyst in Negishi Coupling

Liu

Wang

Zhang

et al. 2009

Chemistry A European J

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“…Chloro and bromo substituted cysteine-reactive probes 8 and 9 were obtained in 82% and 74% yields (Scheme S1). When subjected to sSphos cross-coupling with biotin-boronic acid 3, neither 8 nor 9 afforded detectable lysate labeling (Figure S16), which we ascribe to the different rates of oxidative addition (I>Br>>Cl) 63 and possible halide effects 64,65 from the large excess of chloride ions in buffer, which is consistent with our observation that a large excess of sodium chloride (1 M) completely ablated labeling (Figure S10).…”

Section: Introductionsupporting

confidence: 87%

Suzuki–Miyaura cross-coupling for chemoproteomic applications

Cao¹,

Armenta²,

Boatner³

et al. 2020

Preprint

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Bioorthogonal chemistry is a mainstay of chemoproteomic sample preparation workflows. While numerous transformations are now available, chemoproteomic studies still rely overwhelmingly on copper-catalyzed azide –alkyne cycloaddition (CuAAC) or 'click' chemistry. Here we demonstrate that gel-based activity-based protein profiling (ABPP) and mass-spectrometry-based chemoproteomic profiling can be conducted using Suzuki–Miyaura cross-coupling. We identify reaction conditions that proceed in complex cell lysates and find that Suzuki –Miyaura cross-coupling and CuAAC yield comparable chemoproteomic coverage. Importantly, Suzuki–Miyaura is also compatible with chemoproteomic target deconvolution, as demonstrated using structurally matched probes tailored to react with the cysteine protease caspase-8. Uniquely enabled by the observed orthogonality of palladium-catalyzed cross-coupling and CuAAC, we combine both reactions to achieve dual protein labeling.

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“…Partial conversion to the diarylketone 43 (22% yield) was nevertheless possible upon addition of 1.5–4 equiv. of KI, possibly achieved through a halide exchange process3637. It is not clear why the aryl bromide leads exclusively to the carboxylic acid, but we speculate that after oxidative addition and migratory insertion, a fast reductive elimination provides an acyl bromide38, which is subsequently attacked by the cesium silanolate.…”

Section: Resultsmentioning

confidence: 92%

Cooperative redox activation for carbon dioxide conversion

et al. 2016

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A longstanding challenge in production chemistry is the development of catalytic methods for the transformation of carbon dioxide into useful chemicals. Silane and borane promoted reductions can be fined-tuned to provide a number of C1-building blocks under mild conditions, but these approaches are limited because of the production of stoichiometric waste compounds. Here we report on the conversion of CO2 with diaryldisilanes, which through cooperative redox activation generate carbon monoxide and a diaryldisiloxane that actively participate in a palladium-catalysed carbonylative Hiyama-Denmark coupling for the synthesis of an array of pharmaceutically relevant diarylketones. Thus the disilane reagent not only serves as the oxygen abstracting agent from CO2, but the silicon-containing ‘waste', produced through oxygen insertion into the Si–Si bond, participates as a reagent for the transmetalation step in the carbonylative coupling. Hence this concept of cooperative redox activation opens up for new avenues in the conversion of CO2.

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Halide and pseudohalide effects in Pd-catalysed cross-coupling reactions

Cited by 63 publications

References 80 publications

Identification of a Highly Efficient Alkylated Pincer Thioimido–Palladium(II) Complex as the Active Catalyst in Negishi Coupling

Identification of a Highly Efficient Alkylated Pincer Thioimido–Palladium(II) Complex as the Active Catalyst in Negishi Coupling

Suzuki–Miyaura cross-coupling for chemoproteomic applications

Cooperative redox activation for carbon dioxide conversion

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