A Novel Route to Imidoylbenzotriazoles and Their Application for the Synthesis of Enaminones

Katritzky, Alan R.; Hayden, Amy E.; Kirichenko, Kostyantyn; Pelphrey, Phillip M.; Ji, Yin

doi:10.1021/jo0496594

Cited by 48 publications

(25 citation statements)

References 49 publications

(52 reference statements)

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“…6 Thus it is very important to search for a convenient and efficient method for the synthesis of this type of compounds. 7 Several methods have been developed for their synthesis including the reactions of imidoyl chlorides with acetonyltributyltin in the presence of palladium catalyst, 8 the addition of amines to acylacetylenes, 9 acylation of metalated ketimines using acylbenzotriazoles as acylating agents, 10 the reactions of lithiated enamines with diethyl carbonate or benzyl chloroformate, 11 the addition of ester or amide enolates to nitriles, 12 palladium-assisted amination of α-keto olefins 9 or amination with O-methylhydroxylamines in the presence of base, 13 and the reactions of alkyl azides and β-ketoesters in a one-pot procedure using 10% Pd/C catalyst and hydrogen.…”

Section: Introductionmentioning

confidence: 99%

Cobalt(II) chloride-mediated synthesis of beta-enamino compounds under solvent-free conditions

Zhang¹,

Hu²

2006

J. Braz. Chem. Soc.

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Uma variedade de β-enaminonas e β-enamino ésteres foi sintetizada pela reação de compostos 1,3-dicarbonílicos com aminas na presença de quantidade catalítica de cloreto de cobalto(II), à temperatura ambiente na ausência de solventes. O procedimento experimental é simples e os produtos são isolados em altos rendimentos.A variety of β-enaminones and β-enamino esters can be synthesized by the reaction of 1,3-dicarbonyl compounds with amines in the presence of a catalytic amount of cobalt(II) chloride at room temperature under solvent-free condition. The experiment procedure is simple, and the products are straightforwardly isolated in high yields.Keywords: β-enaminones, β-enamino esters, 1,3-dicarbonyl compounds, amines, cobalt(II) chloride, solvent-free conditions Introduction β-Enaminones have attracted much attention due to the fact that they are important synthons for the synthesis of many biologically active compounds such as dopamine auto-receptor agonists, 1 acetylcholinestersase inhibitors 2 and anticonvulsants. 3 They are also useful intermediates for the preparation of several aminoacids, 4 aminols, 5 peptides and alkaloids. 6 Thus it is very important to search for a convenient and efficient method for the synthesis of this type of compounds. 7 Several methods have been developed for their synthesis including the reactions of imidoyl chlorides with acetonyltributyltin in the presence of palladium catalyst, 8 the addition of amines to acylacetylenes, 9 acylation of metalated ketimines using acylbenzotriazoles as acylating agents, 10 the reactions of lithiated enamines with diethyl carbonate or benzyl chloroformate, 11 the addition of ester or amide enolates to nitriles, 12 palladium-assisted amination of α-keto olefins 9 or amination with O-methylhydroxylamines in the presence of base, 13 and the reactions of alkyl azides and β-ketoesters in a one-pot procedure using 10% Pd/C catalyst and hydrogen.14 However, the most commonly used and straightforward approach for the preparation of these compounds is the direct condensation of β-dicarbonyl compounds and amines, in which the azeotropic removal of water is usually required under reflux using a Dean Stark trap in aromatic solvent. 15 organic transformations will be quite useful. As a part of our ongoing program in developing various new synthetic transformations using cheap and eco-friendly materials as catalysts, 39 we herein wish to report our results on the synthesis of β-enaminones and β-enamino esters using a catalytic amount of CoCl 2 ·6H 2 O at room temperature under solvent-free condition (Scheme 1). Results and DiscussionOur initial studies were focused on the optimization of the reaction conditions for the synthesis of β-enamino esters. Ethyl acetoacetate was chosen as a model substrate for the optimization process. The reaction of ethyl acetoacetate with aniline in the presence of 5 mol% CoCl 2 ·6H 2 O at room temperature, without any solvent, afforded the target ethyl 3-(phenylamino)but-2-enoate (3e) in 95% yield. Lower catalyst loading ca...

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Section: Introductionmentioning

confidence: 99%

Cobalt(II) chloride-mediated synthesis of beta-enamino compounds under solvent-free conditions

Zhang¹,

Hu²

2006

J. Braz. Chem. Soc.

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“…All products gave satisfactory analytical data, which were listed as follows. (2) , g¼74.863(2) , V¼1368.4(3) Å 3 ; T¼293(2) K; l¼0.71073 Å; Z¼4, D calc ¼1.293 g cm À3 ; F(000)¼560, m¼0.085 mm À1 ; crystal size¼0.420Â0.381Â0.207 mm; reflections collected, 7267; unique reflections (R int ¼0.0709), 5029; wR2¼0.1437(all data), R1¼0.0527 (I>2s(I)); Data in the q range 1.87e25.50 were collected at 293 (2) K on a Bruker Apex CCD diffractometer. The structure was solved by direct methods and refined by full-matrix least-squares using all F 2 data.…”

Section: General Proceduresmentioning

confidence: 99%

The facile one-pot synthesis of N-imidoylbenzotriazoles via a Beckmann rearrangement of ketoximes

Liu

Jiang

et al. 2010

Tetrahedron

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“…Uma série de imidoilbenzotriazóis foi preparada por Katritzky et al 19 , reagindo amidas secundárias com 1-cloro-1-H-benzotriazol na presença de trifenilfosfina. Os imidoilbenzotriazóis preparados foram utilizados na síntese de β-enamino cetonas através da substituição da benzotriazoíla com silil enolatos (Esquema 7).…”

Section: Métodos De Preparaçãounclassified

Preparações e aplicações sintéticas recentes de enaminonas

Ferraz¹,

Gonçalo²

2007

Quím. Nova

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A Novel Route to Imidoylbenzotriazoles and Their Application for the Synthesis of Enaminones

Abstract: Reactions of secondary amides 2a-i with 1-chloro-1H-benzotriazole and triphenylphosphine give imidoylbenzotriazoles 3a-i. The treatment of 3a,b,e,g with silyl enol ethers 5a,b in the presence of potassium tert-butoxide provides a new general approach to enaminoketones 6a-h.

Cited by 48 publications

References 49 publications

Cobalt(II) chloride-mediated synthesis of beta-enamino compounds under solvent-free conditions

Cobalt(II) chloride-mediated synthesis of beta-enamino compounds under solvent-free conditions

The facile one-pot synthesis of N-imidoylbenzotriazoles via a Beckmann rearrangement of ketoximes

Preparações e aplicações sintéticas recentes de enaminonas

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