Structure and Mechanism in Ketene Chemistry

Allen, Annette D.; Tidwell, Thomas T.

doi:10.1016/b978-0-12-800256-8.00004-7

Cited by 12 publications

(7 citation statements)

References 230 publications

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“…Ketene chemistry remains a very active area of research worldwide, involving both synthetic and mechanistic studies, and has been extensively reviewed. [3][4][5][6][7][8][9][10][11][12][13][14][15] This review describes the most recent work in the area, which is rich in further opportunities. The organization of this review includes separate headings on ketene preparation and on ketene reactions, but since ketenes are usually short-lived intermediates ketene formation and reactivity are usually inextricably mixed, and examples of one almost invariably contain the other.…”

Section: Introductionmentioning

confidence: 99%

Recent advances in ketene chemistry

Allen¹,

Tidwell²

2016

Arkivoc

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Recent advances in ketene chemistry are reviewed, including synthetic, mechanistic, and computational studies. Topics include ketene structure determination by experimental and theoretical methods, computational studies of bonding in ketenes, spectroscopic properties of ketenes, preparation and formation of ketenes including photochemical and thermal methods, the discovery and observation of ketenes in space, and ketene reactions. The last category includes decarbonylation, cycloadditions with carbon-carbon, carbon-nitrogen, and carbon-oxygen multiple bonds, addition of oxygen, nitrogen, and carbon nucleophiles, and electrophilic additions.

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Section: Introductionmentioning

confidence: 99%

Recent advances in ketene chemistry

Allen¹,

Tidwell²

2016

Arkivoc

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“…Ketenes are characterized by an unusual 'heteroallenic' bond structure, which gives rise to their unique reactivity. 28 The ketene's highest occupied molecular orbital (HOMO) is located perpendicular to the plane of the ketene, while the lowest unoccupied molecular orbital (LUMO) is located within that plane (Scheme 1c). This orientation allows for a large negative charge on the oxygen and β-carbon, while a similarly large positive charge is placed on the α-carbon.…”

Section: Characteristics and Reaction Patterns Of Photogenerated Ketenesmentioning

confidence: 99%

Lighting the way to diverse cyclic architectures: expanding the horizons with photogenerated ketenes in sustainable chemistry

et al. 2023

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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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Structure and Mechanism in Ketene Chemistry

Cited by 12 publications

References 230 publications

Recent advances in ketene chemistry

Recent advances in ketene chemistry

Lighting the way to diverse cyclic architectures: expanding the horizons with photogenerated ketenes in sustainable chemistry

Silylium ion Migration Dominated Hydroamidation of Siloxy-alkynes

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