A Drastic Effect of TEMPO in Zinc‐Catalyzed Stannylation of Terminal Alkynes with Hydrostannanes via Dehydrogenation and Oxidative Dehydrogenation

Kai, Yuichi; Oku, Shinya; Tani, Tomohiro; Sakurai, Kyoko; Tsuchimoto, Teruhisa

doi:10.1002/adsc.201900540

Cited by 15 publications

(12 citation statements)

References 81 publications

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“…After nucleophilic addition to tributyltin fluoride ( 10-236 ), the corresponding products could be produced. Recently, Tsuchimoto et al combined this Cu-catalyzed alkynylstannylation protocol with a Zn-catalyzed stannylation of terminal alkynes . In 2019, Yoshida et al revealed a Cu-catalyzed arylstannylation of arynes with electron-deficient arylstannanes 10-238 (Scheme b) .…”

Section: Transition-metal-catalyzed Reactionsmentioning

confidence: 99%

“…Recently, Tsuchimoto et al combined this Cu-catalyzed alkynylstannylation protocol with a Zn-catalyzed stannylation of terminal alkynes. 857 In 2019, Yoshida et al revealed a Cu-catalyzed arylstannylation of arynes with electron-deficient arylstannanes 10-238 (Scheme 259b). 858 By using copper(I) 2-thiophenecarboxylate (CuTC) as the catalyst, both substituted ortho-stannylbiaryls 10-240 and teraryls 10-241 could be prepared, the mechanistic pathway of which involves either a single or double insertion of arynes into arylstannanes, respectively.…”

Section: Copper-catalyzed/mediated Reactionsmentioning

confidence: 99%

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o-Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors

2021

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Arynes are among the most active organic intermediates and have found numerous applications in expeditious preparation of substituted arenes. In the past 20 years, chemists have witnessed a resurgence in aryne chemistry, which is mainly attributed by the extensive utilization of Kobayashi's method, a fluoride-induced removal of the TMS group with concomitant departure of its ortho OTf group on o-silylaryl triflates. Nowadays, o-silylaryl triflates are the most frequently employed aryne precursors. This review provides an overview of the history of Kobayashi's method, its methodological achievements, and its applications in the synthesis of natural products, bioactive molecules, and polycyclic aromatic hydrocarbons.

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Section: Transition-metal-catalyzed Reactionsmentioning

confidence: 99%

Section: Copper-catalyzed/mediated Reactionsmentioning

confidence: 99%

o-Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors

2021

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“…2 Thus, the Zn (II) ion, being economically viable, naturally available in abundance, and biocompatible, plays a substantial role in synthetic chemistry. [3][4][5][6] Unlike transition metals, zinc-catalyzed reactions are mechanistically distinct for specific reactions such as polymerization, [7][8][9] oxidative coupling reactions, [10][11][12] and dehydrocoupling of alcohols with silanes. [13][14][15] From the synthesis of the first organozinc compound-diethylzinc-from metallic zinc and ethyl iodide by Frankland et al to date, several potential applications of organo-zinc compounds have been reported, demonstrating the evolution of synthetic organic chemistry.…”

Section: Introductionmentioning

confidence: 99%

NHC–Zn alkyl catalyzed cross-dehydrocoupling of amines and silanes

et al. 2023

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“…Stannylation of terminal alkynes with Bu 3 SnH using TEMPO and a Zn catalyst was presented (Scheme b). Reactions proceed via formation of TEMPOSnBu 3 , which transfers the stannyl group to the alkyne through zinc catalysis …”

Section: Oxidation Reactionsmentioning

confidence: 99%

Organic Synthesis Using Nitroxides

Leifert

Studer

2023

Chem. Rev.

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Nitroxides, also known as nitroxyl radicals, are long-lived or stable radicals with the general structure R 1 R 2 N−O • . The spin distribution over the nitroxide N and O atoms contributes to the thermodynamic stability of these radicals. The presence of bulky N-substituents R 1 and R 2 prevents nitroxide radical dimerization, ensuring their kinetic stability. Despite their reactivity toward various transient C radicals, some nitroxides can be easily stored under air at room temperature. Furthermore, nitroxides can be oxidized to oxoammonium salts (R 1 R 2 N�O + ) or reduced to anions (R 1 R 2 N−O − ), enabling them to act as valuable oxidants or reductants depending on their oxidation state. Therefore, they exhibit interesting reactivity across all three oxidation states. Due to these fascinating properties, nitroxides find extensive applications in diverse fields such as biochemistry, medicinal chemistry, materials science, and organic synthesis. This review focuses on the versatile applications of nitroxides in organic synthesis. For their use in other important fields, we will refer to several review articles. The introductory part provides a brief overview of the history of nitroxide chemistry. Subsequently, the key methods for preparing nitroxides are discussed, followed by an examination of their structural diversity and physical properties. The main portion of this review is dedicated to oxidation reactions, wherein parent nitroxides or their corresponding oxoammonium salts serve as active species. It will be demonstrated that various functional groups (such as alcohols, amines, enolates, and alkanes among others) can be efficiently oxidized. These oxidations can be carried out using nitroxides as catalysts in combination with various stoichiometric terminal oxidants. By reducing nitroxides to their corresponding anions, they become effective reducing reagents with intriguing applications in organic synthesis. Nitroxides possess the ability to selectively react with transient radicals, making them useful for terminating radical cascade reactions by forming alkoxyamines. Depending on their structure, alkoxyamines exhibit weak C−O bonds, allowing for the thermal generation of C radicals through reversible C−O bond cleavage. Such thermally generated C radicals can participate in various radical transformations, as discussed toward the end of this review. Furthermore, the application of this strategy in natural product synthesis will be presented.

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A Drastic Effect of TEMPO in Zinc‐Catalyzed Stannylation of Terminal Alkynes with Hydrostannanes via Dehydrogenation and Oxidative Dehydrogenation

Cited by 15 publications

References 81 publications

o-Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors

o-Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors

NHC–Zn alkyl catalyzed cross-dehydrocoupling of amines and silanes

Organic Synthesis Using Nitroxides

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