Base-Mediated Borylsilylation/Silylation of Ammonium Salts with Silylborane

Qi, Wan-Ying; Zhen, Jing-Song; Xu, Xiaohong; Du, Xian; Li, Yihui; Han, Yuling; Guan, Yun-Shi; Wei, Xun; Wang, Ziying; Liang, Guohai; Luo, Yong

doi:10.1021/acs.orglett.1c02066

Cited by 10 publications

(3 citation statements)

References 34 publications

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“…To date, a related functionalization of methyl group on silicon via 1, n -metal migration is limited to a palladium-catalyzed process for a preinstalled MeR 2 Si-group on bromonaphthalenes via 1,5-palladium migration . In this context, as a new entry of 1, n -metal migration using a 3d transition metal, herein we describe the development of a copper-catalyzed regio- and stereoselective synthesis of alkenylsilylmethylboronates , from unsymmetric internal alkynes and silylboronates by formal hydro(borylmethylsilyl)ation − , involving a 1,4-copper migration process from an alkenyl carbon to an alkyl carbon, , which has never been reported for any 3d transition metals (Scheme b). …”

Section: Introductionmentioning

confidence: 97%

Copper-Catalyzed Regio- and Stereoselective Formal Hydro(borylmethylsilyl)ation of Internal Alkynes via Alkenyl-to-Alkyl 1,4-Copper Migration

Moniwa,

Yamanaka,

Shintani

2023

J. Am. Chem. Soc.

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Catalytic reactions involving 1,n-metal migration from carbon to carbon enable a nonclassical way of constructing organic molecular skeletons, rapidly providing complex molecules from relatively simple precursors. By utilization of this attractive feature, a new and efficient synthesis of alkenylsilylmethylboronates has been developed by formal hydro(borylmethylsilyl)ation of unsymmetric internal alkynes with silylboronates under copper catalysis. The reaction proceeds regioselectively and involves an unprecedented alkenyl-to-alkyl 1,4-copper migration. The reaction mechanism has been investigated by a series of kinetic, NMR, and deuterium-labeling experiments.

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Section: Introductionmentioning

confidence: 97%

Copper-Catalyzed Regio- and Stereoselective Formal Hydro(borylmethylsilyl)ation of Internal Alkynes via Alkenyl-to-Alkyl 1,4-Copper Migration

Moniwa,

Yamanaka,

Shintani

2023

J. Am. Chem. Soc.

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“…Organosilicons play crucial roles in organic synthesis, medicine, and materials science. [1][2][3][4][5] Gas chromatography-mass spectrometry (GC-MS) is an essential tool for characterizing organosilicon reagents. 6,7 However, when using Orbitrap GC-MS to measure synthetic compounds containing Si atoms, unexpected ion peaks are often observed in our study.…”

Section: Introductionmentioning

confidence: 99%

“…Organosilicons play crucial roles in organic synthesis, medicine, and materials science 1–5 . Gas chromatography–mass spectrometry (GC–MS) is an essential tool for characterizing organosilicon reagents 6,7 .…”

Section: Introductionmentioning

confidence: 99%

Investigation of unexpected silane ions caused by gas‐phase reactions in Orbitrap gas chromatography–mass spectrometry

Hu,

Chen,

Zhou

et al. 2024

Rapid Comm Mass Spectrometry

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RationaleThe mass spectra of compounds containing dimethyl (phenyl)silyl group (‐SiMe2Ph) sometimes exhibit unusual ion peaks when measured using Orbitrap gas chromatography–mass spectrometry (GC–MS). This would complicate the mass spectra and may limit the matching of spectral data with preexisting resources for compound annotation. These peaks were identified as products from reactions with residual water.MethodsA series of dimethyl (phenyl)silyl compounds were dissolved in methanol and investigated using Orbitrap GC–MS. Certain ions reacted with residual water in the C‐trap. The reaction was confirmed using accurate mass and elemental composition analysis via MS studies, and the active center of the reaction was determined using density functional theory (DFT) calculations.ResultsTwo types of gas‐phase reactions between gaseous water and cations from a series of silanes were identified. DFT calculations indicate that silicon (Si) acts as the active center for these gas‐phase water reactions. Compounds with multiple Si atoms generate a larger number of additional ions, which would complicate the mass spectra. The mass spectra of vinylsilanes and alkylsilanes with ‐SiMe2Ph indicate that the conjugated group linked to ‐SiMe2Ph can affect the water adduction process.ConclusionsSilane ions could react with residual water in the C‐trap of an Orbitrap mass spectrometer. The mass spectra of these compounds may exhibit unexplained peaks arising from gas‐phase reactions. Although these reactions may decrease spectral matching scores for compound annotation, they offer opportunities for systematic investigations into the mechanistic and kinetic aspects of high‐energy ion reactivity.

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Walking Cations: Transition‐Metal Free Benzyl Cation‐Triggered sp² C—H Phosphorylation and Etherification

et al. 2022

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Comprehensive Summary A novel benzyl cation‐triggered site‐selective sp2 C—H phosphorylation and etherification was developed. This reaction was conducted under the transition metal‐free conditions through cation migration via dearomatization. Under the reaction conditions, the derivatives of naphthalenes, benzofurans and benzo[b]thiophenes all can be transformed into the corresponding products in good to excellent yields. It provides a method to construct sp2 C—P and sp2 C—O bonds as well as a new strategy for benzylic activation‐triggered sp2 C—H functionalization.

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Base-Mediated Borylsilylation/Silylation of Ammonium Salts with Silylborane

Cited by 10 publications

References 34 publications

Copper-Catalyzed Regio- and Stereoselective Formal Hydro(borylmethylsilyl)ation of Internal Alkynes via Alkenyl-to-Alkyl 1,4-Copper Migration

Copper-Catalyzed Regio- and Stereoselective Formal Hydro(borylmethylsilyl)ation of Internal Alkynes via Alkenyl-to-Alkyl 1,4-Copper Migration

Investigation of unexpected silane ions caused by gas‐phase reactions in Orbitrap gas chromatography–mass spectrometry

Walking Cations: Transition‐Metal Free Benzyl Cation‐Triggered sp² C—H Phosphorylation and Etherification

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Base-Mediated Borylsilylation/Silylation of Ammonium Salts with Silylborane

Cited by 10 publications

References 34 publications

Copper-Catalyzed Regio- and Stereoselective Formal Hydro(borylmethylsilyl)ation of Internal Alkynes via Alkenyl-to-Alkyl 1,4-Copper Migration

Copper-Catalyzed Regio- and Stereoselective Formal Hydro(borylmethylsilyl)ation of Internal Alkynes via Alkenyl-to-Alkyl 1,4-Copper Migration

Investigation of unexpected silane ions caused by gas‐phase reactions in Orbitrap gas chromatography–mass spectrometry

Walking Cations: Transition‐Metal Free Benzyl Cation‐Triggered sp2 C—H Phosphorylation and Etherification

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Walking Cations: Transition‐Metal Free Benzyl Cation‐Triggered sp² C—H Phosphorylation and Etherification