Baylis-Hillman Chemistry in Aqueous Media: A Fast and Practical Approach to the Azides of Baylis-Hillman Adducts in Solution and on Solid Phase

Patra, Arundhati; Roy, Amrendra Kumar; Batra, Sanjay; Bhaduri, A. P.

doi:10.1055/s-2002-34887

Cited by 16 publications

(16 citation statements)

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“…With this consideration in mind, we prepared a variety of substituted 2‐(azidomethyl)‐3‐phenylpropenoates ( 1 a – 1 k ) according to the reported procedure,15, 16 and subjected them to 2.0 equiv of NBS and visible light irradiation (with a 45 W household fluorescent lamp) in dichloromethane (DCM) under argon atmosphere. The results are summarized in Table 1.…”

Section: Methodsmentioning

confidence: 99%

Vogelspinne zeigt neue Schmerz‐Wege

Groß¹

2016

Chemie in nserer Zeit

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Section: Methodsmentioning

confidence: 99%

Vogelspinne zeigt neue Schmerz‐Wege

Groß¹

2016

Chemie in nserer Zeit

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“…8 We selected azide 2f to optimize the reaction conditions (Scheme 1). Reduction of the ester group in 2f with diisobutylaluminum hydride smoothly produced the alcohol 3f stereoselectively as the E-isomer within 30 minutes.…”

Section: Synthesis Of 7-benzylidene-4678-tetrahydro[123]triazolomentioning

confidence: 99%

“…Synthesis of 7-benzylidene-4,6,7,8-tetrahydro [1,2,3]triazolo[5,1-c] [1,4]oxazepine: We initiated our study with the synthesis of allyl azides via an earlier reported procedure. 8 We selected azide 2f to optimize the reaction conditions (Scheme 1). Reduction of the ester group in 2f with diisobutylaluminum hydride smoothly produced the alcohol 3f stereoselectively as the E-isomer within 30 minutes.…”

mentioning

confidence: 99%

Utility of Allylic Azides for the Synthesis of Fused Triazoles and Tetrazoles via Intramolecular Cycloaddition¹

Mishra¹,

Hutait²,

Bhowmik³

et al. 2010

Synthesis

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The synthesis of a variety of annulated triazoles and tetrazoles from differently substituted allyl azides, afforded from the Baylis-Hillman adduct of acrylates, using intramolecular cycloaddition approach is described.Recent times have witnessed a stupendous increase in the number of applications of azide derivatives for the synthesis of a plethora of 1,2,3-triazole derivatives; this is because they are of use in several spheres including bioconjugation, 2 material, 3 and medicinal chemistry. 4 Generally, syntheses of 1,2,3-triazoles have been achieved either through Husigen 5 or click reactions. 6 Due to the importance of triazoles and their annulated analogues, investigations with newer substrates to accomplish the synthesis of diverse derivatives is an active area of research. We have been interested in the synthesis of heterocycles from intermediates offered via BaylisHillman chemistry and during the course of this program we became interested in the synthesis of annulated 1,2,3-triazoles. The literature includes several strategies for obtaining triazoles using Baylis-Hillman derivatives, which essentially employ intramolecular or intermolecular cycloaddition reactions. 7 We, thus, embarked on an intramolecular cycloaddition approach wherein we utilized the ester moiety to obtain the acetylene or the azide unit for the synthesis of [1,2,3]triazolo[5,1-c][1,4]oxazepines and [1,2,3]triazolo[1,5-a][1,4]diazepines. During the course of the study it became apparent that substrates generated in this work could be extended for the synthesis of an annulated tetrazole system through the cycloaddition reaction. We report results of our studies in this direction. Synthesis of 7-benzylidene-4,6,7,8-tetrahydro[1,2,3]triazolo[5,1-c][1,4]oxazepine:We initiated our study with the synthesis of allyl azides via an earlier reported procedure. 8 We selected azide 2f to optimize the reaction conditions (Scheme 1). Reduction of the ester group in 2f with diisobutylaluminum hydride smoothly produced the alcohol 3f stereoselectively as the E-isomer within 30 minutes. The alcohol 3f was reacted with propargyl bromide in the presence of sodium hydride to yield 4f, which then served as the substrate for intramolecular dipolar cycloaddition. Unfortunately, 4f was found to be unstable and, therefore, it was subjected to further reaction without purification. Refluxing compound 4f in toluene for five hours furnished a mixture of two products which were separated via a careful column chromatography. Based on the spectral analysis, we expected these compounds to be the E-and Z-isomers of the expected annulated triazole 5f. In order to confirm the assigned structure and investigate the relative stereochemistry of these two products, detailed NMR experiments were performed. Combined application of 1 H, 13 C, and 2D NMR (viz. HSQC, HMBC, and NOESY) spectra revealed that the less polar compound was the E-isomer (E)-5f (Figure 1) whereas the polar analogue was the Z-isomer of (Z)-5f ( Figure 2). Scheme 1 Reagents and conditions: (i) NaN 3 , DAB...

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“…The procedure was the same as described in the preparation of 4a with 3d (0.99 g, 3 mmoles) except reaction time (7 hours 15, 52.56, 83.88, 89.13, 122.56, 127.97, 128.82, 129.03, 129.32, 132.74, 136.22, 142.44, 142.65, 167.13, 170.13; ms: m/z (%) 313 (M + , 16), 270 (100), 182 (16), 154 (15).…”

Section: Methyl 3-acetoxy-3-(2-ethynyl)phenyl-2-hydroxy-2-methyleneprmentioning

confidence: 99%

“…The reaction of adducts 2 a-d with acetic anhydride in the presence of catalytic amount of N , N-d i m e t h y laminopyridine (DMAP) in dichloromethane at room temperature gave the Baylis-Hillman acetate adducts 3a-d ( 7 6 -96%). The stereochemistry of the products was established by comparing NMR values of olefinic and methylene protons with literature values [15]. The stereochemistry of the products was established by comparing NMR values of olefinic and methylene protons with literature values [15].…”

mentioning

confidence: 99%

Synthesis of 5H‐1,2,3‐triazolo[4,3‐a][2]benzazepines from the baylis‐hillman adducts of 2‐alkynylbenzaldehydes

Lee

2004

Journal of Heterocyclic Chem

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The facile synthesis of 5H‐1,2,3‐triazolo[4,3‐a][2]benzazepines 5a‐d by the intramolecular 1,3‐dipolar cycloaddition reaction of 2‐alkynylphenylallyl azides 4a‐d is described. The latter were readily obtained from 2‐alkynylbenzaldehydes 1a‐d through the Baylis‐Hillman adducts 2a‐d followed by acetylation to compounds 3a‐d and nucleophilic substitution by azide to compounds 4a‐d.

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Baylis-Hillman Chemistry in Aqueous Media: A Fast and Practical Approach to the Azides of Baylis-Hillman Adducts in Solution and on Solid Phase

Abstract: Fast and practical access to azides of Baylis-Hillman adducts, from the corresponding acetates in aqueous media and in excellent yields is described. The solution phase methodology has been successfully translated to the solid phase for applications toward combinatorial synthesis.

Cited by 16 publications

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Vogelspinne zeigt neue Schmerz‐Wege

Vogelspinne zeigt neue Schmerz‐Wege

Utility of Allylic Azides for the Synthesis of Fused Triazoles and Tetrazoles via Intramolecular Cycloaddition¹

Synthesis of 5H‐1,2,3‐triazolo[4,3‐a][2]benzazepines from the baylis‐hillman adducts of 2‐alkynylbenzaldehydes

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