3-Hydroxy-2-(trialkylsilyl)phenyl Triflate: A Benzyne Precursor Triggered via 1,3-C-sp<sup>2</sup>-to-O Silyl Migration

Kwon, Yong-Ju; Jeon, Young‐Kyo; Sim, Ha-Bin; Oh, In-Young; Shin, Inji; Kim, Won‐Suk

doi:10.1021/acs.orglett.7b03160

Cited by 21 publications

(8 citation statements)

References 35 publications

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“…We have already demonstrated the power of geminal bis(silanes) in organic synthesis by bifunctionalizing the two C–Si bonds . Inspired by these studies, along with Smith’, Takeda’s, our own, and others’ progress in cross-coupling based on Brook rearrangement involving Csp 2 to O -silyl migration, as well as our recent synthesis of 2,6-di(trimethylsilyl) benzaldehyde, we wished to test the scenario in Scheme b. In this pathway, the hydroxyl group in 1 acts as an “on–off–on” switch to control each step in the sequential [1,4]-Csp 2 to O -silyl migration.…”

Section: Introductionmentioning

confidence: 99%

One-Pot Twofold Unsymmetrical C–Si Bond 2,6-Bifunctionalization of Arenes via Sequential [1,4]-Csp² to O-Silyl Migration

Wang

et al. 2019

J. Org. Chem.

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Twofold unsymmetrical C−Si bond bifunctionalization of 2,6-di(trimethylsilyl) benzyl alcohols has been achieved in one pot via sequential [1,4]-Csp 2 to O-silyl migration. The hydroxyl group functions as an "on−off−on" switch to control two successive silyl migrations, and 4,7dimethyl-o-phenanthroline ligand favors cleavage of the endocyclic C−Si bond. Diverse Csp 3 /Csp 3 or Csp 2 /Csp 3 electrophiles can be installed at the 2-and 6-positions. This approach was used to chemoselectively functionalize the three C−Si bonds of 2,4,6-tri(trimethylsilyl) benzyl alcohol, transforming it into isochroman derivatives. The approach even works as a five-component reaction to construct complex symmetric structures.

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Section: Introductionmentioning

confidence: 99%

One-Pot Twofold Unsymmetrical C–Si Bond 2,6-Bifunctionalization of Arenes via Sequential [1,4]-Csp² to O-Silyl Migration

Wang

et al. 2019

J. Org. Chem.

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“…The thus generated 3‐trialkylsiloxybenzynes can, for example, be regioselectively trapped by aniline, as shown with the formation of compound 82 , or undergo a [4+2] cycloaddition reaction with 2,5‐dimethylfuran, leading to the bridged tricyclic product 84 (Scheme 30). [58] These examples showcase the power of this chemistry, which found many applications in synthesis [59] …”

Section: C(sp2)−si Bond Functionalization Through Endocyclic Cleavagementioning

confidence: 93%

C(sp²)−Si Bond Functionalization through Intramolecular Activation by Alkoxides

et al. 2021

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Organosilicon reagents are invaluable tools in the hands of the modern chemist that allow accomplishing a number of synthetically useful transformations. While some are standard reactions, others are more complex transformations, such as the Brook rearrangement and its variants. This carbon‐to‐oxygen silyl migration represents a privileged method to generate transient carbanionic species well suited to undergo functionalization upon electrophilic substitution in the presence of an electrophile. This minireview focuses on recent advances in C(sp2)−Si bond functionalization through intramolecular activation by alkoxides. The key elements of reactivity will be highlighted in the introduction to allow the proper understanding of the migration process. Then, an overview of the reactivity of substrates incorporating the C(sp2)−Si motif and their synthetic applications will be provided.

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“…Other aryne precursors, including heteroaromatic ones, have also been reported to-date [ 139 , 140 , 141 , 142 , 143 , 144 , 145 ]. The aryne cycloaddition approach also found its application in the synthesis of biologically active indazoles [ 146 ].…”

Section: Azoles With Two Heteroatomsmentioning

confidence: 99%

Diazocarbonyl and Related Compounds in the Synthesis of Azoles

et al. 2021

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Diazocarbonyl compounds have found numerous applications in many areas of chemistry. Among the most developed fields of diazo chemistry is the preparation of azoles from diazo compounds. This approach represents a useful alternative to more conventional methods of the synthesis of azoles. A comprehensive review on the preparation of various azoles (oxazoles, thiazoles, imidazoles, pyrazoles, triazoles, and tetrazoles) from diazocarbonyl and related compounds is presented for the first time along with discussion of advantages and disadvantages of «diazo» approaches to azoles.

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3-Hydroxy-2-(trialkylsilyl)phenyl Triflate: A Benzyne Precursor Triggered via 1,3-C-sp²-to-O Silyl Migration

Cited by 21 publications

References 35 publications

One-Pot Twofold Unsymmetrical C–Si Bond 2,6-Bifunctionalization of Arenes via Sequential [1,4]-Csp² to O-Silyl Migration

One-Pot Twofold Unsymmetrical C–Si Bond 2,6-Bifunctionalization of Arenes via Sequential [1,4]-Csp² to O-Silyl Migration

C(sp²)−Si Bond Functionalization through Intramolecular Activation by Alkoxides

Diazocarbonyl and Related Compounds in the Synthesis of Azoles

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3-Hydroxy-2-(trialkylsilyl)phenyl Triflate: A Benzyne Precursor Triggered via 1,3-C-sp2-to-O Silyl Migration

Cited by 21 publications

References 35 publications

One-Pot Twofold Unsymmetrical C–Si Bond 2,6-Bifunctionalization of Arenes via Sequential [1,4]-Csp2 to O-Silyl Migration

One-Pot Twofold Unsymmetrical C–Si Bond 2,6-Bifunctionalization of Arenes via Sequential [1,4]-Csp2 to O-Silyl Migration

C(sp2)−Si Bond Functionalization through Intramolecular Activation by Alkoxides

Diazocarbonyl and Related Compounds in the Synthesis of Azoles

Contact Info

Product

Resources

About

3-Hydroxy-2-(trialkylsilyl)phenyl Triflate: A Benzyne Precursor Triggered via 1,3-C-sp²-to-O Silyl Migration

One-Pot Twofold Unsymmetrical C–Si Bond 2,6-Bifunctionalization of Arenes via Sequential [1,4]-Csp² to O-Silyl Migration

One-Pot Twofold Unsymmetrical C–Si Bond 2,6-Bifunctionalization of Arenes via Sequential [1,4]-Csp² to O-Silyl Migration

C(sp²)−Si Bond Functionalization through Intramolecular Activation by Alkoxides