Ketene dithioacetals in organic synthesis

Huang, Lifeng; Wu, Jinjing; Hu, Jingang; Bi, Yicheng; Huang, Dayun

doi:10.1016/j.tetlet.2019.151363

Cited by 27 publications

(15 citation statements)

References 102 publications

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“…[29] The current existing report mainly concentrated on carbon substituted ketene species. [25,30] According to our calculations, silver-ketene is only 1.1 kcal/mol less stable than A-int1 (see Figure 2, A-int5). If there is a reagent that stabilizes the TIPSOTf, the π-acid and σ-acid exchange scheme may be a relatively easy strategy to syn-thesis highly active silver-ketenes.…”

Section: Comparation Between Silver-ketene and Ynolatesmentioning

confidence: 60%

Mechanism of Silver-Catalyzed [2+2] Cycloaddition between Siloxy-Alkynes and Carbonyl Compound: A Silylium Ion Migration Approach

Wang¹,

Jiang²,

Liang³

et al. 2021

Chinese Journal of Organic Chemistry

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cycloaddition between siloxy-alkynes and α,β-unsaturated carbonyl compound remains controversial. Based on density functional theory (DFT) calculation, it is revealed that Ag ＋ activate siloxy-alkyne into silver-ketene and silylium ion (TIPS ＋ ) in this reaction. TIPS ＋ then promote [2＋2] cycloaddition between α,β-unsaturated carbonyl compound and silver-ketene to form cyclobutane-intermediate, which undergos TIPS ＋ migration and transforms into final product. The mechanism of Ag ＋ catalyzed olefination of aldehydes using siloxy-alkynes was also investigated, the results showed that TIPS ＋ migration also took place in this reaction. In the two reactions studied, Ag ＋ interacts with π-bond of siloxy-alkynes and triggers TIPS ＋ migration, which offers alternative solution to silylium-catalyzed reaction. As similarity of ynolates, silver-ketenes are more stable, which can undergo 1,4-nucleophilic addition with α,βunsaturated compound. For [2＋2] cycloaddition, catalytic variant is rather limited, this work provides a different perspective to obtain four-membered ring products or its ring-open derivates.

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Section: Comparation Between Silver-ketene and Ynolatesmentioning

confidence: 60%

Mechanism of Silver-Catalyzed [2+2] Cycloaddition between Siloxy-Alkynes and Carbonyl Compound: A Silylium Ion Migration Approach

Wang¹,

Jiang²,

Liang³

et al. 2021

Chinese Journal of Organic Chemistry

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“…Hydroamination or hydroamidation of allenes is quite easy for high activity of the two cumulated π-bond 1,12,21 . Ketene is analogs of allenes, it's very important intermediate in the organic chemistry [36][37][38][39] . Transition metal promoted nucleophilic attack favors take place in the intersection point of the two π-bond.…”

Section: Silylium Ion Migration Leads To Final Productmentioning

confidence: 99%

“…If the hydrogen atom of ketene was changed into halogen or other groups, this reaction may also take place, and the regio-selective is steric-controlled (scheme 3a). Synthesizing substituted-ketenes has been extensively studied [36][37][38] , and silyl-imines can be easily obtained (One of the feasible approaches is reaction between Chlorotriisopropylsilane (ClTIPS) and amide with base as catalyst in low temperature). So, our calculation provides a general approach to obtain substituted enamides (Scheme 3).…”

Section: A General Way To Synthesis Substituted Enamidesmentioning

confidence: 99%

Silylium ion Migration Dominated Hydroamidation of Siloxy-alkynes

Wang¹,

Jiang²,

Fan³

2021

Preprint

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Intermolecular hydroamidation of internal alkynes has been a long-standing challenge, one of the most successful examples so far is silver-catalyzed hydroamidation of siloxy-alkynes for which meet the standards of atom economic and mild reaction conditions of ideal hydroamidation. However, the mechanism of this reaction remains controversy. Using density function theory (DFT), we revealed that the reaction takes place through a silylium ion migration mediated hydroamidation (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+ activate the siloxy-alkyne into silylium ion and silver-ketene through p-π conjugate effect, the silylium ion then act as catalyst. According to our calculation, the scopes of alkynes in this reaction may be extend to silyl-substituted ynamines or silyl-substituted ynamides, and the scopes of amide maybe expanded into p-π conjugate system such as diazoles, diazepines and so on. Our calculations also reveal a concise way to construct substituted enamides through Ag+ catalyzed nucleophilic addition between ketenes (or ketene imines) and silyl-substituted p-π conjugate system such as silyl-imines, silyl-diazoles.

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“…These compounds readily react with various nucleophilic reagents, so they are often used for the synthesis of a number of heterocyclic compounds, such as pyrans, pyrroles, thiophenes, pyrazoles, pyridines and pyrimidines, etc. [1,2]. Ketene-S,S-acetals also show biological activity, they found an application in agriculture and medicine [1,2].…”

Section: Introductionmentioning

confidence: 99%

“…[1,2]. Ketene-S,S-acetals also show biological activity, they found an application in agriculture and medicine [1,2].…”

Section: Introductionmentioning

confidence: 99%

The Aminometylation of 4-(Alkylthio)-6-amino-2-oxo(thioxo)-1,2-dihydropyridine-3,5-dicarbonitriles

Khrapova

Ryzhkova

Доценко

et al. 2020

The 24th International Electronic Conference on Synthetic Organic Chemistry

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Ketene dithioacetals in organic synthesis

Cited by 27 publications

References 102 publications

Mechanism of Silver-Catalyzed [2+2] Cycloaddition between Siloxy-Alkynes and Carbonyl Compound: A Silylium Ion Migration Approach

Mechanism of Silver-Catalyzed [2+2] Cycloaddition between Siloxy-Alkynes and Carbonyl Compound: A Silylium Ion Migration Approach

Silylium ion Migration Dominated Hydroamidation of Siloxy-alkynes

The Aminometylation of 4-(Alkylthio)-6-amino-2-oxo(thioxo)-1,2-dihydropyridine-3,5-dicarbonitriles

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