Facile Synthesis of a “Ready to Use” Precursor of Porphobilinogen and Its Amino Acid Derivatives

Pissot‐Soldermann, Carole; Vallinayagam, Ramakrishnan; Tzouros, Manuel; Neier, Reinhard

doi:10.1021/jo702319n

Cited by 9 publications

(4 citation statements)

References 34 publications

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“…Removal of solvent in vacuum, followed by isolation using HPLC, yielded 2-hydroxy-2-methyl-4-oxo-4-phenylbutyronitrile 3 (4 mg, 0.021 mmol, 3% yield) and ( E )-2-methyl-4-oxo-4-phenyl-but-2-enenitrile 4 (2 mg, 0.011 mmol, 1.6% yield) and recovered the starting material. The spectroscopic characterizations of 3 and 4 fit with those in the literature. , …”

Section: Methodssupporting

confidence: 61%

“…The spectroscopic characterizations of 3 and 4 fit with those in the literature. 45 26 Stock solutions of 1 in methanol or acetonitrile were prepared with spectroscopic-grade solvents such that the solutions had an absorption between 0.2 and 0.8 at the excitation wavelengths. Solutions were purged with nitrogen or oxygen for at least 15 min.…”

Section: Methodsmentioning

confidence: 99%

“…The spectroscopic characterizations of 3 and 4 fit with those in the literature. 45,46 Compound 3. 47 or an excimer laser (308 nm, 17 ns).…”

Section: Methodsmentioning

confidence: 99%

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Triplet Sensitized Photolysis of a Vinyl Azide: Direct Detection of a Triplet Vinyl Azide and Nitrene

Rajam

Jadhav

et al. 2014

J. Org. Chem.

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Photolysis of vinylazide 1, which has a built-in acetophenone triplet sensitizer, in argon-saturated toluene results in azirine 2, whereas irradiation in oxygen-saturated toluene yields cyanide derivatives 3 and 4. Laser flash photolysis of azide 1 in argon-saturated acetonitrile shows formation of vinylnitrene 1c, which has a λmax at ∼300 nm and a lifetime of ∼1 ms. Vinylnitrene 1c is formed with a rate constant of 4.25 × 10(5) s(-1) from triplet 1,2-biradical 1b. Laser flash photolysis of 1 in oxygen-saturated acetonitrile results in 1c-O (λmax = 430 nm, τ ≈ 420 μs acetonitrile). Density functional theory (DFT) calculations were used to aid in the characterization of the intermediates formed upon irradiation of azide 1 and to validate the proposed mechanism for its photoreactivity.

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Section: Methodssupporting

confidence: 61%

Section: Methodsmentioning

confidence: 99%

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Triplet Sensitized Photolysis of a Vinyl Azide: Direct Detection of a Triplet Vinyl Azide and Nitrene

Rajam

Jadhav

et al. 2014

J. Org. Chem.

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“…Pale yellow solid; yield 0.68 g (50%); mp 150-151°C. IR (KBr): 1628, 1608, 1516, 1448, 1420, 1372, 1252, 1208, 1172, 1044 4, 26.3, 48.0, 56.0, 56.1, 104.1, 108.0, 109.7, 110.1, 123.6, 127.7, 131.0, 135.4, 146.1, 149.6, 166.7. MS (EI, 70 eV): m/z (%) = 270 (30) [M + ], 255 (100), 240 (33), 211 (27), 182 (11), 170 (16).…”

Section: -({1mentioning

confidence: 99%

Furan Ring Opening-Pyrrole Ring Closure: Simple Route to 5-Alkyl-2-(aminomethyl)pyrroles

Бутин¹,

Nevolina²,

Shcherbinin³

et al. 2010

Synthesis

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A simple route to 5-alkyl-2-(aminomethyl)pyrroles is proposed that is based on hydrolytic ring opening of 5-alkylfurfurylamines followed by pyrrole ring closure under Paal-Knorr conditions.2-(Aminomethyl)pyrroles have a broad range of biological activities 1 and have been shown to be potential antiinflammatory, 2 analgesic, 3 antidepressant, 4 antipsychotic, 5 or antitumor agents. 6 2-(Aminomethyl)pyrroles have also been used in the treatment of attention-deficit hyperactive disorder; 7 they have also been used in the preparation of conformationally restricted peptidomimetics 8,9 and anionbinding receptors, 9,10 and for the synthesis of pyrrolodiazepines 11-13 and other bioactive molecules containing pyrrole units annulated to other heterocycles. 1i,13-15 The 2-(aminomethyl)pyrrole moiety is present in a variety of natural compounds such as porphobilinogen, an important intermediate in the biosynthesis of porphyrins, corrins, and chlorophylls. 16 2-(Aminomethyl)pyrroles can be transformed into porphyrinogens, 17 pyrrodimethanes, 18 porphyrins, or porphocyanins. 19 2-(Aminomethyl)pyrroles are usually synthesized by the reduction of the corresponding oximes, 1b,g,6a,9,10,20 nitriles, 1e,6a,19c,20b,21 azides, 1d,8b,12,14,22 or amides. 5a Other approaches to 2-(aminomethyl)pyrroles include the reductive amination of pyrrole-2-carbaldehydes, 8d,23 the transformation of pyrrole-2-carbaldehydes into imines followed by addition of nucleophilic reagents, 24 aminoalkylation of pyrroles, 22b,25 nucleophilic substitution of bromine in 2-(bromomethyl)pyrroles, 5a,18a,26 and a variety of intramolecular condensation reactions. 8g,27 One of the oldest and best-known methods for the synthesis of pyrroles is the Paal-Knorr reaction, i.e., the reaction of 1,4-diketones or their analogues with primary amines or ammonia. 28 However, the application of this approach to the synthesis of 2-(aminomethyl)pyrroles is very restricted, 1i,11,13 because of difficulties in preparing the necessary 1,4-diketones. 1-Phthalimido-2,5-diketones have been synthesized by a benzoin condensation-like addition of aldehydes to vinyl ketones in the presence of thiazolium salts as catalysts, 29 or by a three-step transformation of 2-(phthalimidomethyl)furans through formation of the corresponding 2,5-dimethoxy-2,5-dihydrofurans, ring opening, and double-bond hydrogenation. 11 An alternative route to these aminodiketones involves the reaction of N-(tert-butoxycarbonyl)glycine with potassium ethyl malonate followed by alkylation of the intermediate with a bromomethyl ketone. 1i 1,4-Diketones can also be prepared by acid-catalyzed cleavage of a furan ring. 30 When the starting furan contains a substituent that is appropriate for further transformation into an aminoalkyl group, a common sequence that involves cleavage of the furan ring followed by closure of the pyrrole ring can be used to provide an efficient synthesis of 2-(aminomethyl)pyrroles. Here, we describe an application of this approach to the transformation of 5-alkylfurfurylamines into the c...

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Metal‐Free Regioselective β‐Alkylation of Pyrroles with Carbonyl Compounds and Hydrosilanes: Use of a Brønsted Acid as a Catalyst

Nomiyama

Tsuchimoto

2014

Adv Synth Catal

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Facile Synthesis of a “Ready to Use” Precursor of Porphobilinogen and Its Amino Acid Derivatives

Cited by 9 publications

References 34 publications

Triplet Sensitized Photolysis of a Vinyl Azide: Direct Detection of a Triplet Vinyl Azide and Nitrene

Triplet Sensitized Photolysis of a Vinyl Azide: Direct Detection of a Triplet Vinyl Azide and Nitrene

Furan Ring Opening-Pyrrole Ring Closure: Simple Route to 5-Alkyl-2-(aminomethyl)pyrroles

Metal‐Free Regioselective β‐Alkylation of Pyrroles with Carbonyl Compounds and Hydrosilanes: Use of a Brønsted Acid as a Catalyst

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