Staudinger reaction in the series of 4-diazotetrahydrofuran-3-ones: Effect of substituents in the diazo and phosphine components

Rodina, L. L.; Galiullina, S. V.; Matyushina, N. V.; Nikolaev, V. A.

doi:10.1134/s1070428007120275

Cited by 5 publications

(4 citation statements)

References 5 publications

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“…First, using compound 4 we attempted to perform the most characteristic reactions of diazo ketones with preservation of the azirine ring. The most useful reactions of diazo ketones are (a) the Wolff rearrangement, , (b) metal-catalyzed cyclopropanation of unsaturated compounds and insertion into C–H bonds, , (c) reaction with acids, which is a very useful method for the site-selective introduction of halogen and other heteroatomic functional groups into carbonyl compounds, , (d) reactions leading to heterocycles either via successive formation of carbene/carbenoid, ylide and its 1,3-cyclization on a carbonyl group, or 1,3-dipolar cycloaddition of a diazo group to an activated CC double bond, , (e) reaction of diazo ketones with triphenylphosphane leading to azirinylphosphazines, which can be used as a method of storage of unstable diazo compounds or for their purification because the starting diazo compound can be liberated from phosphazine by reaction with methyl iodide. ,, Unexpectedly, we failed to obtain a product typical for the diazo ketone Wolff rearrangement . Only tarring of the reaction mixture was observed when compound 4a was refluxed in methanol in the presence of Ag 2 O or heated in α,α,α-trifluorotoluene in the presence of benzylamine.…”

Section: Results and Discussionmentioning

confidence: 99%

“…According to the 1 H, 31 P, and 13 C spectra, dissolution of 6 in CDCl 3 is accompanied by partial dissociation to starting diazo compound 4 and triphenylphosphane ( 6a : 4a = 1:0.14 and 6b : 4h = 1:0.18). Such dissociation is characteristic of phosphazines …”

Section: Experimental Sectionmentioning

confidence: 99%

“…Such dissociation is characteristic of phosphazines. 16 1-(3-Phenyl-2H-azirin-2-yl)-2-((triphenyl-λ 5 -phosphanylidene)hydrazono)ethan-1-one (6a). Light yellow solid, mp 127−129 °C (Et 2 O/hexane), yield 425 mg (95%).…”

Section: -Bromo-1-(3-(4-bromophenyl)-2h-azirin-2-yl)ethan-1-one (5c)mentioning

confidence: 99%

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2-Diazoacetyl-2H-azirines: Source of a Variety of 2H-Azirine Building Blocks with Orthogonal and Domino Reactivity

2018

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A synthesis of 2-diazoacetyl-2 H-azirines was developed starting from 2 H-azirine-2-carbonyl chlorides, generated by Fe(II)-catalyzed isomerization of 5-chloroisoxazoles. 2-Diazoacetyl-2 H-azirines easily undergo reactions characteristic of α-diazo ketones with preservation of the azirine ring. Reactions with hydrohalogenic, carboxylic, and p-toluenesulfonic acids provide novel 1-(3-aryl-2 H-azirin-2-yl)-2-halo- and 2-(R-oxy)ethan-1-ones in good yields. The synthesized 2 H-azirines can offer many possibilities for chemical manipulation in heterocyclic synthesis, due to the presence of highly reactive azirine and the exocyclic C(O)-CHN or C(O)-CHX functionalities, which can show orthogonal or domino reactivity. The synthetic usefulness of the developed building blocks was demonstrated by the preparation of new types of heterocyclic dyads (azirine-oxazole, azirine-pyrazoline, azirine-thiazole, azirine-oxirane, pyrrole-oxazole) as well as an azirine chalcone analogue, 2-azidoacetyl-2 H-azirine, and 2-diazoacetylaziridine derivatives.

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Section: Results and Discussionmentioning

confidence: 99%

Section: Experimental Sectionmentioning

confidence: 99%

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2-Diazoacetyl-2H-azirines: Source of a Variety of 2H-Azirine Building Blocks with Orthogonal and Domino Reactivity

2018

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“…The reaction is a fast one and gives phosphazines 77 in good yields. The treatment of the latter with aldehydes delivers bis-hydrazones 78 ( Scheme 47 ) [ 79 ].…”

Section: Cyclic α-Diazo Ketonessmentioning

confidence: 99%

Preparation and Synthetic Applications of Five-to-Seven-Membered Cyclic α-Diazo Monocarbonyl Compounds

Zhukovsky¹,

Dar’in

Bakulina

et al. 2022

Molecules

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Diazo Strategy for the Synthesis of Pyridazines: Pivotal Impact of the Configuration of the Diazo Precursor on the Process

Nikolaev

Cantillo

Kappe

et al. 2015

Chemistry A European J

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Phosphazenes of vinyldiazocarbonyl compounds having cis stereochemistry of the functional groups on the vinyl bond readily produce pyridazines by a diaza-Wittig process, whereas their counterparts with trans configuration remain intact under similar reaction conditions. Upon UV irradiation trans-phosphazenes furnish pyridazines through a tandem trans-to-cis isomerization followed by intramolecular cyclization. At elevated temperatures trans-(triphenyl)phosphazenes dissociate to give the initial vinyldiazo compounds, which produce pyrazoles in high yields. The first theoretical study on the mechanism of the diaza-Wittig process by DFT calculations at the M06-2X/6-31G(d) level of theory suggest that for the cis-phosphazenes a rapid tandem [2+2] cycloaddition/cycloelimination process with low energy barriers is preferred over trans isomers.

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Staudinger reaction in the series of 4-diazotetrahydrofuran-3-ones: Effect of substituents in the diazo and phosphine components

Cited by 5 publications

References 5 publications

2-Diazoacetyl-2H-azirines: Source of a Variety of 2H-Azirine Building Blocks with Orthogonal and Domino Reactivity

2-Diazoacetyl-2H-azirines: Source of a Variety of 2H-Azirine Building Blocks with Orthogonal and Domino Reactivity

Preparation and Synthetic Applications of Five-to-Seven-Membered Cyclic α-Diazo Monocarbonyl Compounds

Diazo Strategy for the Synthesis of Pyridazines: Pivotal Impact of the Configuration of the Diazo Precursor on the Process

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