A facile, one pot method for the synthesis of 4-acyl-1,2-dihydro-3-benzazepines, based on the ring expansion of natural and synthetic 3,4-dihydroisoquinoline pseudo bases

Карцев, В. Г.; Зубенко, А. А.; Морковник, А. С.; Диваева, Л. Н.

doi:10.1016/j.tetlet.2015.10.103

Cited by 27 publications

(8 citation statements)

References 41 publications

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“…In the conditions 1, the reaction of the N‐substituted 3‐chloroacetylindole 2 c and p‐methoxyphenacylbromide ( 2 h ) with 1 gave the mixture (≈ 1 : 4) of the corresponding products 6 and 3 (Table ). But in conditions 2, only normal products 3c and 3 h were formed in these reactions with yields 83 and 73 %, respectively. In contrast to the haloketone 2 c , all N‐unsubstituted 3‐chloroacetylindoles (compounds 2 a,b,d ‐ g ) in the conditions 1 give only the rearranged products 6 a,b,d ‐ g , usually in good yields (Table ).…”

Section: Methodsmentioning

confidence: 91%

“…3‐Benzazepine moiety is an important pharmacophore represented in many biologically active compounds and drugs (see review and the literature cited in our previous work). However, many functionalized 3‐benzazepines, particularly those that have acyl group in the azepine ring, remain poorly characterized.…”

Section: Methodsmentioning

confidence: 99%

“…However, many functionalized 3‐benzazepines, particularly those that have acyl group in the azepine ring, remain poorly characterized. Recently, we reported a new and simple method for the synthesis of practically unknown 4‐acyl‐1,2‐dihydro‐3‐benzazepines from 3,4‐dihydroisoquinolinium pseudo bases by the six‐to‐seven heterocyclic ring expansion reaction with various α‐haloketones ( 2 ) in the presence of weak bases. The proposed reaction mechanism is depicted in Scheme using isoquinoline alkaloid cotarnine ( 1 ) as an example.…”

Section: Methodsmentioning

confidence: 99%

“…The proposed reaction mechanism is depicted in Scheme using isoquinoline alkaloid cotarnine ( 1 ) as an example. This mechanism involves three stages: N‐acylmethylation of the open‐chain tautomer of the substrate 1B , cyclization of N‐acylmethyl derivatives, such as 4 , into 5‐hydroxy‐4‐acyl‐1,2,3,4‐tetrahydro‐3‐benzazepines (such as 5 ), and dehydration of the latter …”

Section: Methodsmentioning

confidence: 99%

“… A Mechanism of the ring expansion reaction of cotarnine ( 1 ) with haloketones 2 proposed in the work.…”

Section: Methodsmentioning

confidence: 99%

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Unusual 1,2‐Acyl Rearrangement Accompanying Ring Expansion Reaction of Alkaloid Cotarnine under the Action of α‐Haloketones: a New Route to 5‐Acyl‐1,2‐dihydro‐3‐benzazepine Moiety

et al. 2016

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The ring expansion reaction of the isoquinoline alkaloid cotarnine with α‐haloketones which normally leads to the formation of 4‐acyl‐7,8‐metylenedioxy‐1,2‐dihydro‐3‐benzazepines, in some cases, occurs with an unusual, non‐acid‐catalytic 1,2‐acyl rearrangement. As a result, corresponding 5‐acyl isomers are formed. A carbocation mechanism of the rearrangement was proposed. It involves formation of 4‐acyl‐5‐hydroxy‐7,8‐metylenedioxy‐1,2,3,4‐tetrahydro‐3‐benzazepines and their dissociation (as leuko bases) into corresponding benzazepine carbocations. As it follows from DFT calculations, these carbocations are prone to almost barrierless intracationic 1,2‐acyl group migration with conversion into corresponding isomeric carbocations. At the last stage of the reaction, these cations are deprotonated into final rearranged compounds.

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Section: Methodsmentioning

confidence: 91%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

“… A Mechanism of the ring expansion reaction of cotarnine ( 1 ) with haloketones 2 proposed in the work.…”

Section: Methodsmentioning

confidence: 99%

See 3 more Smart Citations

Unusual 1,2‐Acyl Rearrangement Accompanying Ring Expansion Reaction of Alkaloid Cotarnine under the Action of α‐Haloketones: a New Route to 5‐Acyl‐1,2‐dihydro‐3‐benzazepine Moiety

et al. 2016

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Graphene Oxide Decorated SiO₂/Fe₃O₄ as a Recyclable Catalyst for the Green Synthesis of Novel Thiazinoazepines via Multicomponent Reaction of Isatoic Anhydrides: Cytotoxic Activity and Theoretical Study

Mohammadi,

Azizi,

Hossaini

2024

Applied Organom Chemis

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This work investigated the use of a complex technique including isatoic anhydrides, α‐haloketones, electron‐deficient acetylenic compounds, ammonium acetate, and isothiocyanates in a water‐based solution at normal room temperature in the presence of SiO2/Fe3O4@Graphene Oxide. The goal was to generate novel thiazinoazepine molecules with significant yields. The thiazinoazepines that have been synthesized contain NH functional groups with acidic protons and demonstrate notable antioxidant activity. The (3‐(4,5‐Dimethylthiazol‐2‐yl)‐2,5‐Diphenyltetrazolium Bromide), MTT assay was utilized to evaluate the cytotoxicity of all the synthesized compounds in vitro against cancer cell lines (MCF‐7 and A549) as well as normal cell lines). Cytotoxicity refers to the ability of a compound to kill cells. The derivative 6e was shown to be the most potent cytotoxic agent, similar to doxorubicin in its lack of selectivity. Alternatively, compound 6b might be considered as a compound that is equally effective but more selective than doxorubicin. Quantum chemical approaches utilizing density functional theory have been utilized to enhance comprehension of reaction mechanisms. The used technology for synthesizing thiazinoazepines provides several advantages, including rapid reaction kinetics, outstanding product yield, and straightforward product isolation.

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Metal‐Free Activation of a C(sp)−H Bond of Aryl Acetylenes

Rout

Parida

Florent

et al. 2016

Chemistry A European J

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C(sp)-H Bond activation of acetylene molecule still remains a challenge for synthetic organic chemists. In practice, acetylenes are activated by strong bases and metals. The first example for activating acetylenic protons under base and metal-free conditions is reported here. It involves a general method for synthesizing propargylic derivatives of cotarnine. An array of tetrahydroisoquinolines alkaloids was synthesized by C(sp)-H bond activation of aromatic acetylenes with cotarnine at room temperature. A DFT-based mechanism is proposed for the reaction.

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A facile, one pot method for the synthesis of 4-acyl-1,2-dihydro-3-benzazepines, based on the ring expansion of natural and synthetic 3,4-dihydroisoquinoline pseudo bases

Cited by 27 publications

References 41 publications

Unusual 1,2‐Acyl Rearrangement Accompanying Ring Expansion Reaction of Alkaloid Cotarnine under the Action of α‐Haloketones: a New Route to 5‐Acyl‐1,2‐dihydro‐3‐benzazepine Moiety

Unusual 1,2‐Acyl Rearrangement Accompanying Ring Expansion Reaction of Alkaloid Cotarnine under the Action of α‐Haloketones: a New Route to 5‐Acyl‐1,2‐dihydro‐3‐benzazepine Moiety

Graphene Oxide Decorated SiO₂/Fe₃O₄ as a Recyclable Catalyst for the Green Synthesis of Novel Thiazinoazepines via Multicomponent Reaction of Isatoic Anhydrides: Cytotoxic Activity and Theoretical Study

Metal‐Free Activation of a C(sp)−H Bond of Aryl Acetylenes

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A facile, one pot method for the synthesis of 4-acyl-1,2-dihydro-3-benzazepines, based on the ring expansion of natural and synthetic 3,4-dihydroisoquinoline pseudo bases

Cited by 27 publications

References 41 publications

Unusual 1,2‐Acyl Rearrangement Accompanying Ring Expansion Reaction of Alkaloid Cotarnine under the Action of α‐Haloketones: a New Route to 5‐Acyl‐1,2‐dihydro‐3‐benzazepine Moiety

Unusual 1,2‐Acyl Rearrangement Accompanying Ring Expansion Reaction of Alkaloid Cotarnine under the Action of α‐Haloketones: a New Route to 5‐Acyl‐1,2‐dihydro‐3‐benzazepine Moiety

Graphene Oxide Decorated SiO2/Fe3O4 as a Recyclable Catalyst for the Green Synthesis of Novel Thiazinoazepines via Multicomponent Reaction of Isatoic Anhydrides: Cytotoxic Activity and Theoretical Study

Metal‐Free Activation of a C(sp)−H Bond of Aryl Acetylenes

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Product

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Graphene Oxide Decorated SiO₂/Fe₃O₄ as a Recyclable Catalyst for the Green Synthesis of Novel Thiazinoazepines via Multicomponent Reaction of Isatoic Anhydrides: Cytotoxic Activity and Theoretical Study