Investigating Direct Alkynylation at the Bridgehead of Bicyclic Cages Using Silver(I) Acetylides

Pouwer, Rebecca H.; Harper, Jason B.; Vyakaranam, Kamesh; Michl, Josef; Williams, Craig M.; Jessen, Carsten; Bernhardt, Paul V.

doi:10.1002/ejoc.200600701

Cited by 27 publications

(21 citation statements)

References 68 publications

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“…Substitution of a boron-bound proton with an electrophile is usually very facile, and occasionally, other kinds of 25 172, Ag + R -95 171 1, A, PhI a A: n-BuLi, ZnCl2, [PdCl2(PPh3)2]; R -) phenylacetylide. 16 substituents can be replaced as well.…”

Section: Electrophilicmentioning

confidence: 99%

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Chemistry of the Carba-closo-dodecaborate(−) Anion, CB₁₁H₁₂^-

2006

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Section: Electrophilicmentioning

confidence: 99%

“…In the order of increasing energy, the occupied valence MOs of 1 are classified as a cluster bonding set (1-4), an exo bonding set (5-16), and a frontier set (17)(18)(19)(20)(21)(22)(23)(24)(25). Electrostatic potential (B3LYP/6-31+G(d)) around 1 and 16.…”

Section: Molecular Orbitalsmentioning

confidence: 99%

Chemistry of the Carba-closo-dodecaborate(−) Anion, CB₁₁H₁₂^-

2006

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“…4‐Methyl‐1‐(2‐phenylethynyl) BCO 135 was synthesized from 1‐iodo‐4‐methylBCO 131 d through reaction with silver(I) phenylacetylide in anhydrous pyridine under argon at 150 °C in 31 % yield. However, these reaction conditions were only successful for this compound, as attempts to react silver(I) phenylacetylide with 1,4‐diiodoBCO and methyl 4‐iodoBCO‐1‐carboxylate failed …”

Section: Reactivity and Manipulation Of The Bridgehead Carbon Centermentioning

confidence: 99%

Nonconjugated Hydrocarbons as Rigid‐Linear Motifs: Isosteres for Material Sciences and Bioorganic and Medicinal Chemistry

Locke

Bernhard

Senge

2019

Chemistry A European J

192

143

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Nonconjugated hydrocarbons, like bicyclo[1.1.1]pentane, bicyclo[2.2.2]octane, triptycene, and cubane are a unique class of rigid linkers. Due to their similarity in size and shape they are useful mimics of classic benzene moieties in drugs, so‐called bioisosteres. Moreover, they also fulfill an important role in material sciences as linear linkers, in order to arrange various functionalities in a defined spatial manner. In this Review article, recent developments and usages of these special, rectilinear systems are discussed. Furthermore, we focus on covalently linked, nonconjugated linear arrangements and discuss the physical and chemical properties and differences of individual linkers, as well as their application in material and medicinal sciences.

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“…INS spectra of metal−acetylide, silver, 25,26 silver/copper, 27 copper, 28,29 and gold 30−34 complexes have been widely reported. The bands seen in the difference spectra of (100%) C 2 H 2 − background were compared to that of Au−CC−H modeled as an isolated molecule, an adsorbed molecule on a single carbon atom of a graphene sheet (to model the carbon Fitting with multiple Au−Cl paths was attempted for all spectra.…”

Section: Acs Catalysismentioning

confidence: 99%

Deactivation of a Single-Site Gold-on-Carbon Acetylene Hydrochlorination Catalyst: An X-ray Absorption and Inelastic Neutron Scattering Study

et al. 2018

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Single-site Au species supported on carbon have been shown to be the active sites for acetylene hydrochlorination. The evolution of these single-site species has been monitored by Au L 3 X-ray absorption spectroscopy (XAS). Alternating between a standard reaction mixture of HCl/C 2 H 2 and the single reactants has provided insights into the reaction mechanism and catalyst deactivation processes. We demonstrate that oxidative addition of HCl across an Au(I) chloride species requires concerted addition with C 2 H 2 , in accordance with both the XAS measurements of Au oxidation state and the reaction kinetics being first order with respect to each reactant. Excess C 2 H 2 changes the Au speciation and results in the formation of oligomeric acetylene species which were detected by inelastic neutron scattering. Catalyst deactivation at extended reaction times can be correlated with the formation of metallic Au particles. These Au(0) species generated during the sequential gas experiments, or after prolonged reaction times, results in the analysis of the normalized near-edge white line intensity becoming an unsuitable guide for identifying the active Au species, affecting the strong correlation between normalized white line height and VCM productivity usually observed in the active catalyst. Thus, a combination of scanning transmission electron continued...

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Investigating Direct Alkynylation at the Bridgehead of Bicyclic Cages Using Silver(I) Acetylides

Cited by 27 publications

References 68 publications

Chemistry of the Carba-closo-dodecaborate(−) Anion, CB₁₁H₁₂^-

Chemistry of the Carba-closo-dodecaborate(−) Anion, CB₁₁H₁₂^-

Nonconjugated Hydrocarbons as Rigid‐Linear Motifs: Isosteres for Material Sciences and Bioorganic and Medicinal Chemistry

Deactivation of a Single-Site Gold-on-Carbon Acetylene Hydrochlorination Catalyst: An X-ray Absorption and Inelastic Neutron Scattering Study

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Investigating Direct Alkynylation at the Bridgehead of Bicyclic Cages Using Silver(I) Acetylides

Cited by 27 publications

References 68 publications

Chemistry of the Carba-closo-dodecaborate(−) Anion, CB11H12-

Chemistry of the Carba-closo-dodecaborate(−) Anion, CB11H12-

Nonconjugated Hydrocarbons as Rigid‐Linear Motifs: Isosteres for Material Sciences and Bioorganic and Medicinal Chemistry

Deactivation of a Single-Site Gold-on-Carbon Acetylene Hydrochlorination Catalyst: An X-ray Absorption and Inelastic Neutron Scattering Study

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Product

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Chemistry of the Carba-closo-dodecaborate(−) Anion, CB₁₁H₁₂^-

Chemistry of the Carba-closo-dodecaborate(−) Anion, CB₁₁H₁₂^-