4-Halo-2-azabuta-1,3-dienes as intermediates in the rhodium carbenoid-initiated transformation of 2-halo-2H-azirines into 2,3-dihydroazetes and 2,5-dihydrooxazoles

Smetanin, Ilia A.; Новиков, Михаил С.; Ростовский, Николай В.; Khlebnikov, Alexander F.; Старова, Галина Л.; Yufit, Dmitry S.

doi:10.1016/j.tet.2015.05.022

Cited by 41 publications

(23 citation statements)

References 43 publications

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“…For example, dihydroazete 21 was obtained only from azadiene E-20, while its Z isomer was found to be inactive in the cyclization (Scheme 3) [29]. 4,4-Disubstituted 2-azabuta-1,3-dienes can be generated by the reactions of azirines or isoxazoles with diazocarbonyl compounds under rhodium catalysis [30,31] (Scheme 4). It was found that a prerequisite for the 1,4-electrocyclization of the resulting 2-azabuta-1,3-dienes 26 is the presence of two electron-withdrawing groups at C1.…”

Section: 4-electrocyclization Of Azabutadienesmentioning

confidence: 99%

“…In most cases, the cyclization reactions occur only at elevated temperatures in reversible fashion. 4-Halo-substituted azadienes 26 with the E configuration of the C=C bond were used to explore the influence of the substituents on the azadiene-dihydroazete equilibrium in C 6 D 6 at 100 • C [31]. It was found that replacing iodine with chlorine led to a change in the azadiene/dihydroazete ratio from 2.6:1 to 1:1.3.…”

Section: 4-electrocyclization Of Azabutadienesmentioning

confidence: 99%

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Electrocyclizations of Conjugated Azapolyenes Produced in Reactions of Azaheterocycles with Metal Carbenes

2021

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Conjugated azapolyenes (azabuta-1,3-dienes, aza-/diaza-/oxaza-/oxadiazahexa-1,3,5-trienes) are highly reactive in electrocyclization reactions, which makes them convenient precursors for the synthesis of a wide range of four-, five-, and six-membered nitrogen heterocycles that are of relevance for medicinal chemistry. Ring opening reactions of 2H-azirines and azoles containing an N–N or N–O bond, initiated by a transition metal carbene, have become increasingly important in recent years, since they easily allow the generation of azapolyenes with different numbers of double bonds and heteroatoms in various positions. This review summarizes the literature, published mainly in the last decade, on the synthetic and mechanistic aspects of electrocyclizations of azapolyenes generated by the carbene method.

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Section: 4-electrocyclization Of Azabutadienesmentioning

confidence: 99%

Section: 4-electrocyclization Of Azabutadienesmentioning

confidence: 99%

Electrocyclizations of Conjugated Azapolyenes Produced in Reactions of Azaheterocycles with Metal Carbenes

2021

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“…compound in Rh II -catalyzed carbene ylide formation 16 and carbene X-H insertion 17 reactions. Padwa and co-workers also reported reactions of 1 and its bromo derivative as halo ketone with various nucleophiles, including thiourea.…”

Section: Syn Thesismentioning

confidence: 99%

Realizing the Trifunctional Potential of Alkyl 4-Chloro-2-diazo-3-oxobutanoates: Convenient Assembly of 6,7-Dihydro-4H-[1,2,3]triazolo[5,1-c][1,4]thiazine Core

et al. 2020

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The first example of exploiting the trifunctional character of alkyl 4-chloro-2-diazo-3-oxobutanoates in the reactions with vicinal N,S-bis-nucleophiles leading to the formation of bicyclic 6,7-dihydro-4H-[1,2,3]triazolo[5,1-c][1,4]thiazines is presented. The key to the successful realization of the atom-economical synthetic strategy is the initial S N 2 event, which facilitates the subsequent domino 1,2,3-triazole formation via the Wolff reaction. Equally important is the choice of sodium acetate as the base: acetic acid formed in the course of the initial nucleophilic substitution acts as an efficient catalyst for the Wolff reaction, which suppresses the competing, unwanted fragmentation path (observed when other bases are used).

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“…The study of the reactivity of these compounds showed that they can be used to prepare other functionalized 2 H -azirines [15,16], but they can also lead to the synthesis of other interesting structures such as quinoxalines [15], functionalized 1,3-oxazoles [17,18], 1-aminovinyl derivatives [16], 4-halo-2-azabuta-1,3-dienes, and 2,3-dihydroazetes [19,20].…”

Section: Introductionmentioning

confidence: 99%

Synthesis of New 2-Halo-2-(1H-tetrazol-5-yl)-2H-azirines via a Non-Classical Wittig Reaction

et al. 2015

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Abstract:The synthesis and reactivity of tetrazol-5-yl-phosphorus ylides towards N-halosuccinimide/TMSN 3 reagent systems was explored, opening the way to new haloazidoalkenes bearing a tetrazol-5-yl substituent.These compounds were obtained as single isomers, except in one case.X-ray crystal structures were determined for three derivatives, establishing that the non-classical Wittig reaction leads to the selective synthesis of haloazidoalkenes with (Z)-configuration.The thermolysis of the haloazidoalkenes afforded new 2-halo-2-(tetrazol-5-yl)-2H-azirines in high yields. Thus, the reported synthetic methodologies gave access to important building blocks in organic synthesis, vinyl tetrazoles and 2-halo-2-(tetrazol-5-yl)-2H-azirine derivatives.

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4-Halo-2-azabuta-1,3-dienes as intermediates in the rhodium carbenoid-initiated transformation of 2-halo-2H-azirines into 2,3-dihydroazetes and 2,5-dihydrooxazoles

Cited by 41 publications

References 43 publications

Electrocyclizations of Conjugated Azapolyenes Produced in Reactions of Azaheterocycles with Metal Carbenes

Electrocyclizations of Conjugated Azapolyenes Produced in Reactions of Azaheterocycles with Metal Carbenes

Realizing the Trifunctional Potential of Alkyl 4-Chloro-2-diazo-3-oxobutanoates: Convenient Assembly of 6,7-Dihydro-4H-[1,2,3]triazolo[5,1-c][1,4]thiazine Core

Synthesis of New 2-Halo-2-(1H-tetrazol-5-yl)-2H-azirines via a Non-Classical Wittig Reaction

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