Strained benzene derivatives by copper-catalyzed tert-butylation

Kuenzer, H.; Berger, Stefan

doi:10.1021/jo00217a045

Cited by 13 publications

(5 citation statements)

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“…For general information, see the ESI. ‡ Compounds 5a, 12,16 5'a, 17 5b, 12,15b,18 5c, 19 5d, 12,18a,20 5e, 18a,21 5f, 5'f, 22 5g, 23 5'g, 23a 5h, 12,24 5'h, 24 5i, 25 nBuLi (≈ 2.0 M solution in hexanes, 0.900 equiv, 2.70 mmol) was added dropwise, over 1 min, into a solution of Ti(OiPr) 4 (0.600 equiv, 1.80 mmol) in dry THF (4.0 mL), in a flame-dried 10 mL microwave vial, under argon at 0 °C. After 5 min of stirring at 0 °C, the alkyne substrate (1.00 equiv, 3.00 mmol) was then added dropwise.…”

Section: Methodsmentioning

confidence: 99%

Can the Ti(OiPr)₄/nBuLi combination of reagents function as a catalyst for [2+2+2] alkyne cyclotrimerisation reactions?

Siemiaszko

Six

2018

New J. Chem.

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Section: Methodsmentioning

confidence: 99%

Can the Ti(OiPr)₄/nBuLi combination of reagents function as a catalyst for [2+2+2] alkyne cyclotrimerisation reactions?

Siemiaszko

Six

2018

New J. Chem.

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“…GCMS analysis showed two principle components in addition to Cp‘H, with (M) + m / z 246 and elution times and fragmentation patterns consistent with isomeric tri- tert -butylbenzenes. The isomers were present in approximately a 1:1 ratio and accounted for most of the remainder of the starting material …”

Section: Methodsmentioning

confidence: 99%

Hydrogen for Fluorine Exchange in CH₄_-_xF_x by Monomeric [1,2,4-(Me₃C)₃C₅H₂]₂CeH: Experimental and Computational Studies

et al. 2005

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The monomeric metallocenecerium hydride, Cp'(2)CeH (Cp' = 1,2,4-tri-tert-butylcyclopentadienyl), reacts instantaneously with CH(3)F, but slower with CH(2)F(2), to give Cp'(2)CeF and CH(4) in each case, a net H for F exchange reaction. The hydride reacts very slowly with CHF(3), and not at all with CF(4), to give Cp'(2)CeF, H(2), and 1,2,4- and 1,3,5-tri-tert-butylbenzene. The substituted benzenes are postulated to result from trapping of a fluorocarbene fragment derived by alpha-fluoride abstraction from Cp'(2)CeCF(3). The fluoroalkyl, Cp'(2)CeCF(3), is generated by reaction of Cp'(2)CeH and Me(3)SiCF(3) or by reaction of the metallacycle, [(Cp')(Me(3)C)(2)C(5)H(2)C(Me(2))CH(2)]Ce, with CHF(3), and its existence is inferred from the products of decomposition, which are Cp'(2)CeF, the isomeric tri-tert-butylbenzenes and in the case of Me(3)SiCF(3), Me(3)SiH. The fluoroalkyls, Cp'(2)CeCH(2)F and Cp'(2)CeCHF(2), generated from the metallacycle and CH(3)F and CH(2)F(2), respectively, are also inferred by their decomposition products, which are Cp'(2)CeF, CH(2), and CHF, respectively, which are trapped. DFT(B3PW91) calculations have been carried out to examine several reaction paths that involve CH and CF bond activation. The calculations show that the CH activation by Cp(2)CeH proceeds with a low barrier. The carbene ejection and trapping by H(2) is the rate-determining step, and the barrier parallels that found for reaction of H(2) with CH(2), CHF, and CF(2). The barrier of the rate-determining step is raised as the number of fluorines increases, while that of the CH activation path is lowered as the number of fluorines increases, which parallels the acidity.

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“…2,5‐Di‐ tert ‐butylphenol (15) [63] . Reaction was performed following the general procedure at 90 mA and 0.3 mL/min flowrate for 133.2 minutes.…”

Section: Methodsmentioning

confidence: 99%

Electrochemical Hydroxylation of Electron‐Rich Arenes in Continuous Flow

et al. 2022

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Dedicated to Laura Ošeka, who was born during the preparation of the manuscript for this article and helped to write it.Electrochemical hydroxylation of arenes by trifluoroacetic acid provides a straightforward access to aryl oxygen compounds under the mild and environmental benign reaction conditions. Harmful and pollutant stoichiometric amounts of oxidation reagents and the use of metal-catalysts can be avoided. Herein, we present a novel method for the synthesis of hydroxylated products from electron-rich arenes that was achieved by the implementation of a continuous-flow setup. The continuous nature of the process allowed to fine-tune the reactions conditions in order to prevent the decomposition of the sensitive products expanding the reaction scope beyond electron-poor and neutral arenes that were previously reported in the batch processes. Thus, synthetically valuable hydroxylated arenes were obtained in good yields with the residence time just over a minute. In order to demonstrate the reliability and the efficiency of the electrochemical flow setup, a scale up experiment was also performed.

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Strained benzene derivatives by copper-catalyzed tert-butylation

Cited by 13 publications

References 0 publications

Can the Ti(OiPr)₄/nBuLi combination of reagents function as a catalyst for [2+2+2] alkyne cyclotrimerisation reactions?

Can the Ti(OiPr)₄/nBuLi combination of reagents function as a catalyst for [2+2+2] alkyne cyclotrimerisation reactions?

Hydrogen for Fluorine Exchange in CH₄_-_xF_x by Monomeric [1,2,4-(Me₃C)₃C₅H₂]₂CeH: Experimental and Computational Studies

Electrochemical Hydroxylation of Electron‐Rich Arenes in Continuous Flow

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Strained benzene derivatives by copper-catalyzed tert-butylation

Cited by 13 publications

References 0 publications

Can the Ti(OiPr)4/nBuLi combination of reagents function as a catalyst for [2+2+2] alkyne cyclotrimerisation reactions?

Can the Ti(OiPr)4/nBuLi combination of reagents function as a catalyst for [2+2+2] alkyne cyclotrimerisation reactions?

Hydrogen for Fluorine Exchange in CH4-xFx by Monomeric [1,2,4-(Me3C)3C5H2]2CeH: Experimental and Computational Studies

Electrochemical Hydroxylation of Electron‐Rich Arenes in Continuous Flow

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Can the Ti(OiPr)₄/nBuLi combination of reagents function as a catalyst for [2+2+2] alkyne cyclotrimerisation reactions?

Can the Ti(OiPr)₄/nBuLi combination of reagents function as a catalyst for [2+2+2] alkyne cyclotrimerisation reactions?

Hydrogen for Fluorine Exchange in CH₄_-_xF_x by Monomeric [1,2,4-(Me₃C)₃C₅H₂]₂CeH: Experimental and Computational Studies