Efficient and Selective Synthesis of <i>E</i>‐Vinylamines <i>via</i> Tungsten(0)‐Catalyzed Hydroamination of Terminal Alkynes

Kocięcka, Paulina; Czeluśniak, Izabela; Szymańska-Buzar, Teresa

doi:10.1002/adsc.201400568

Cited by 9 publications

(3 citation statements)

References 45 publications

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“…It has been suggested that dirhodium vinylidene 334 , an isolable intermediate, is a catalyst resting state and exists in equilibrium with the mononuclear vinylidene complex 333 that enters into the catalytic cycle . Another intermolecular hydroamination reaction employing a W(CO) 4 (piperidine) 2 catalyst has been reported producing enamine products with good yield …”

Section: Catalytic Reactions Of Metal-complexed Alkenylidenes: Carbon...mentioning

confidence: 99%

Transition Metal Vinylidene- and Allenylidene-Mediated Catalysis in Organic Synthesis

2019

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With their mechanistic novelty and various modalities of reactivity, transition metal unsaturated carbene (alkenylidene) complexes have emerged as versatile intermediates for new reaction discovery. In particular, the past decade has witnessed remarkable advances in the chemistry of metal vinylidenes and allenylidenes, leading to the evolution of a diverse array of new catalytic transformations that are mechanistically distinct from those developed in the previous two decades. This review aims to provide a survey of the recent achievements in the development of organic reactions that make use of transition metal alkenylidenes as catalytic intermediates and their applications to organic synthesis.

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Section: Catalytic Reactions Of Metal-complexed Alkenylidenes: Carbon...mentioning

confidence: 99%

Transition Metal Vinylidene- and Allenylidene-Mediated Catalysis in Organic Synthesis

2019

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“…Significant progress has been made in catalyzed hydroamidation, and high levels of chemo-, regio-, and stereo-selectivity have been reported 4 , 11 – 13 . However, currently reported examples are mainly centered on hydroamidation 14 – 17 of terminal alkynes 9 , 18 .…”

Section: Introductionmentioning

confidence: 99%

Silylium ion migration dominated hydroamidation of siloxy-alkynes

2022

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The mechanism of silver-catalyzed hydroamidation of siloxy-alkynes reaction remains controversial. Using density functional theory (DFT), we revealed that the reaction takes place through a silylium ion migration mediated hydroamination (SMH) pathway. The SMH pathway goes through two steps, the first step is Ag+ promoted proton and silylium ion exchange between siloxy-alkynes and amide, leading to ketene and silyl-imines, the second step is Ag+ catalyzed nucleophilic addition between ketene and silyl-imines, following with a silylium ion migration afford the final product. In this reaction, Ag+ activates the siloxy-alkyne into silylium ion (TIPS+) and silver-ketene through the p–π conjugate effect, the silylium ion then catalyzes the reaction. According to our calculation, the scopes of alkynes in this reaction may be extended to silyl-substituted ynamines or silyl-substituted ynamides. The scopes of amide may be extended into the p–π conjugate system such as diazoles, diazepines, etc. Our calculations also reveal a concise way to construct enamides through Ag+ catalyzed nucleophilic addition between substituted-ketenes and silyl-substituted p–π conjugate system.

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“…In this context, hydroamination of alkynes has been studied extensively to prepare nitrogen-containing molecules with high atom efficiency, but there are still limitations in the functional group tolerance and the substrate scope. For example, few reports have been made on anti-Markovnikov addition of secondary amines to alkylacetylenes, which are relatively less electrophilic than arylacetylenes. − …”

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confidence: 99%

2:1 versus 1:1 Coupling of Alkylacetylenes with Secondary Amines: Selectivity Switching in 8-Quinolinolato Rhodium Catalysis

et al. 2021

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Both 2:1 and 1:1 couplings of alkylacetylenes with secondary amines were achieved using 8-quinolinolato rhodium catalysts and CsF. The 2:1/1:1 selectivity was switched by choosing the reaction solvent. In DMA, an unprecedented 2:1 coupling reaction of alkylacetylenes with amines proceeded to give 2-aminodiene products. One-pot 2:1 coupling/reduction provided rapid access to various allylamines, while one-pot coupling/hydrolysis gave enones as products. In toluene, anti-Markovnikov hydroamination occurred under relatively mild conditions to give 1:1 coupling products.

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Efficient and Selective Synthesis of E‐Vinylamines via Tungsten(0)‐Catalyzed Hydroamination of Terminal Alkynes

Cited by 9 publications

References 45 publications

Transition Metal Vinylidene- and Allenylidene-Mediated Catalysis in Organic Synthesis

Transition Metal Vinylidene- and Allenylidene-Mediated Catalysis in Organic Synthesis

Silylium ion migration dominated hydroamidation of siloxy-alkynes

2:1 versus 1:1 Coupling of Alkylacetylenes with Secondary Amines: Selectivity Switching in 8-Quinolinolato Rhodium Catalysis

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