Oligosilanes as Silyl Radical Precursors through Oxidative Si−Si Bond Cleavage Using Redox Catalysis

Yu, Xia; Lübbesmeyer, Maximilian; Studer, Armido

doi:10.1002/ange.202011738

Cited by 13 publications

(4 citation statements)

References 89 publications

(24 reference statements)

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“…The reaction tolerates carboxylic acids with various ring sizes, cyclic or acyclic ethers and protected amines (PG = Boc (tert-butoxycarbonyl), Bac (tert-butylaminocarbonyl), Piv (pivaloyl), Cbz (carboxybenzyl)), and even drugs and peptides as nucleophiles in the context of late stage functionalisation. Finally, Studer and co-workers developed a BCB hydrosilylation reaction to give cyclobutyl silanes 68 80 . A photoredox-catalysed oxidation of disilanes generated a silyl radical, which could add to BCBs as well as electron-deficient alkenes.…”

Section: Substituted Cyclobutanes By Strain-release Ring-openingmentioning

confidence: 99%

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Bicyclobutanes as unusual building blocks for complexity generation in organic synthesis

Golfmann

Walker

2023

Commun Chem

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Bicyclobutanes are among the most highly strained isolable organic compounds and their associated low activation barriers to reactivity make them intriguing building-blocks in organic chemistry. In recent years, numerous creative synthetic strategies exploiting their heightened reactivity have been presented and these discoveries have often gone hand-in-hand with the development of more practical routes for their synthesis. Their proclivity as strain-release reagents through their weak central C–C bond has been harnessed in a variety of addition, rearrangement and insertion reactions, providing rapid access to a rich tapestry of complex molecular scaffolds. This review will provide an overview of the different options available for bicyclobutane synthesis, the main classes of compounds that can be prepared from bicyclobutanes, and the associated modes of reactivity used.

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Section: Substituted Cyclobutanes By Strain-release Ring-openingmentioning

confidence: 99%

“…Jui and co-workers [79] Silanes: Studer and co-workers [80] Alkanes by dechlorination: Lin and co-workers [46] Ethers and amines by decarboxylation: Cintrat and co-workers [47] D: Umpolung BCB activation: Gryko and co-workers [48] Conditions…”

Section: N-methyl Anilinesmentioning

confidence: 99%

Bicyclobutanes as unusual building blocks for complexity generation in organic synthesis

Golfmann

Walker

2023

Commun Chem

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“…On the other hand, Studer and coworkers reported that nucleophilic silyl radicals were generated via single-electron oxidation of disilanes by Ir-based photo-redox catalysts under visible light irradiation. 21 Even though Au has a thermodynamically stable metallic state, cationic Au species with a high oxidation potential (E Au(0)/Au(I) = +1.69 V vs. SHE) 22 are known to form at the interface between their nanoparticles and metal oxides. 23 As HAADF-STEM image of Au/ZrO2 shown in Figure 2a, Au nanoparticles are highly dispersed at the surface of ZrO2 with their mean diameter of 2.9 nm.…”

Section: Pd Znmentioning

confidence: 99%

Diverse Alkyl–Silyl Cross-Coupling via Homolysis of Unactivated C(sp3)–O Bonds with the Cooperation of Gold and Amphoteric Oxides

Miura

Doi

Yasui

et al. 2022

Preprint

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Since C(sp3)–O bonds are a ubiquitous chemical motif in both natural and artificial organic molecules, the universal transformation of C(sp3)–O bonds will be a key technology for achieving carbon neutrality. We report herein that gold nanoparticles supported on amphoteric metal oxides efficiently generated alkyl radicals via homolysis of unactivated C(sp3)–O bonds, which consequently promoted C(sp3)–Si bond formation to give diverse organosilicon compounds. A wide array of esters and ethers which are either commercially available or easily synthesized from alcohols participated in the heterogeneous gold-catalyzed silylation by disilanes to give diverse alkyl-, allyl-, benzyl- and allenylsilanes in high yields. In addition, this novel reaction technology for C(sp3)–O bond transformation could be applied to the upcycling of polyesters, i.e., the degradation of polyester and the synthesis of organosilanes were realized concurrently by the unique catalysis of supported gold nanoparticles. Mechanistic studies corroborated the notion that the generation of alkyl radicals is involved in C(sp3)–Si coupling and the cooperation of gold and an acid-base pair on amphoteric oxides is responsible for the homolysis of stable C(sp3)–O bonds. The high reusability and air-tolerance of the heterogeneous gold catalysts as well as a simple, scalable, and green reaction system not only enabled the practical synthesis of diverse organosilicon compounds, but also contributed to the progress toward carbon neutrality.

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“…2, d). 57,58 A few years ago, Grubbs and coworkers developed a base-promoted silylation of C-H bonds suggesting a radical addition-dehydrogenation process (Fig. 2, e).…”

mentioning

confidence: 99%

Electrifying synthesis of organosilicon compounds – from electrosynthesis to electrocatalysis

Kuciński

2023

Inorg. Chem. Front.

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Oligosilanes as Silyl Radical Precursors through Oxidative Si−Si Bond Cleavage Using Redox Catalysis

Cited by 13 publications

References 89 publications

Bicyclobutanes as unusual building blocks for complexity generation in organic synthesis

Bicyclobutanes as unusual building blocks for complexity generation in organic synthesis

Diverse Alkyl–Silyl Cross-Coupling via Homolysis of Unactivated C(sp3)–O Bonds with the Cooperation of Gold and Amphoteric Oxides

Electrifying synthesis of organosilicon compounds – from electrosynthesis to electrocatalysis

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