Aziridines-IV Catalytic decomposition of phenyldiazomethane in Schiff's bases

Bartnik, R.; Mlostoń, Grzegorz

doi:10.1016/s0040-4020(01)83511-0

Cited by 44 publications

(14 citation statements)

References 15 publications

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“…diphenylaziridines were reported to react with dimethyl fumarate and dimethyl maleate stereoselectively yielding the corresponding diastereoisomeric products [6]. A similar observation was made for cis- N-methyl-2,3-diphenylaziridine (cis-1a) [7]. Analogous studies performed with C≡C, C=O, and C=S (thioketones) dipolarophiles showed that the formation of the corresponding five-membered cycloadducts occurs stereoselectively, i.e., the intermediate azomethine ylides…”

mentioning

confidence: 67%

Concerted vs. Non‐Concerted 1,3‐Dipolar Cycloadditions of Azomethine Ylides to Electron‐Deficient Dialkyl 2,3‐Dicyanobut‐2‐enedioates

Khlebnikov

Konev

Virtsev

et al. 2014

Helvetica Chimica Acta

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The quantum-chemical calculations of the thermal ring opening of 1-methyl-2,3-diphenyl-and 1,2,3-triphenylaziridine with formation of the corresponding azomethine ylides of S-, U-, and W-type as well as their cycloaddition to dimethyl acetylenedicarboxylate (DMAD) and dimethyl 2,3-dicyanobut-2-enedioate, were performed at the DFT B3LYP/6-31G(d) level of theory with the PCM solvation model. The calculations are in complete accordance with experimental results and explain the switch from the concerted to the non-concerted pathway depending on substituents in the dipolarophile and the ylide. It was found that strong electron-withdrawing substituents in dipolarophiles, such as in dialkyl dicyanobutenedioates, significantly reduce the barrier for the formation of zwitterionic intermediates in the reaction of azomethine ylides with such dipoles. This can render the stepwise cycloaddition competitive with the concerted one. However, the concertedness of the cycloaddition even to dipolarophiles with several electron-withdrawing substituents is governed by a fine balance of electronic and steric effects in both ylide and dipolarophile counterparts. The hypothesis that introduction of substituents in the azomethine ylide that destabilize the positive charge in a corresponding zwitterion will favor the concerted cycloaddition even with dialkyl dicyanobutenedioates was tested theoretically and experimentally.

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confidence: 67%

Concerted vs. Non‐Concerted 1,3‐Dipolar Cycloadditions of Azomethine Ylides to Electron‐Deficient Dialkyl 2,3‐Dicyanobut‐2‐enedioates

Khlebnikov

Konev

Virtsev

et al. 2014

Helvetica Chimica Acta

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“…The catalytic decomposition of diazoalkanes in the presence of a Schiff's base is a convenient source of azomethine ylides (Scheme 59) [138]. The copper(I) bromide-catalyzed decomposition of phenyldiazomethane 207 produces a carbene-Cu(I) complex 209.…”

Section: Diazoalkanesmentioning

confidence: 99%

1,3-Dipolar Cycloaddition Reactions of Azomethine Ylides with Carbonyl Dipolarophiles Yielding Oxazolidine Derivatives

Meyer

Ryan

2016

Molecules

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Abstract:We provide a comprehensive account of the 1,3-dipolar cycloaddition reactions of azomethine ylides with carbonyl dipolarophiles. Many different azomethine ylides have been studied, including stabilized and non-stabilized ylides. Of the carbonyl dipolarophiles, aldehydes including formaldehyde are the most studied, although there are now examples of cycloadditions with ketones, ketenes and carboxyl systems, in particular isatoic anhydrides and phthalic anhydrides. Intramolecular cycloadditions with esters can also occur under certain circumstances. The oxazolidine cycloadducts undergo a range of reactions triggered by the ring-opening of the oxazolidine ring system.

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“…In our earlier reports, reactions of N-substituted aziridines with acetylenes [10], alkenes [10] [11], carbonyl [11] [12], and thiocarbonyl groups [10] [13 -15] were described. All of the reported reactions yielded [2 þ 3]-cycloadducts with the expected configuration, i.e., cis-2,3-disubstituted aziridines led to trans-disubstituted products, and trans-2,3-disubstituted aziridines gave cis-disubstituted cycloadducts.…”

mentioning

confidence: 99%

Thermal [2+3]‐Cycloadditions of trans‐1‐Methyl‐2,3‐diphenylaziridine with CS and CC Dipolarophiles: An Unexpected Course with Dimethyl Dicyanofumarate

Mlostoń

Urbaniak

Domagała³

et al. 2009

Helvetica Chimica Acta

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The thermal reaction of trans-1-methyl-2,3-diphenylaziridine (trans-1a) with aromatic and cycloaliphatic thioketones 2 in boiling toluene yielded the corresponding cis-2,4-diphenyl-1,3-thiazolidines cis-4 via conrotatory ring opening of trans-1a and a concerted [2 þ 3]-cycloaddition of the intermediate (E,E)-configured azomethine ylide 3a (Scheme 1). The analogous reaction of cis-1a with dimethyl acetylenedicarboxylate (5) gave dimethyl trans-2,5-dihydro-1-methyl-2,5-diphenylpyrrole-3,4-dicarboxylate (trans-6) in accord with orbital-symmetry-controlled reactions (Scheme 2). On the other hand, the reactions of cis-1a and trans-1a with dimethyl dicyanofumarate (7a), as well as that of cis-1a and dimethyl dicyanomaleate (7b), led to mixtures of the same two stereoisomeric dimethyl 3,4-dicyano-1-methyl-2,5-diphenylpyrrolidine-3,4-dicarboxylates 8a and 8b (Scheme 3). This result has to be explained via a stepwise reaction mechanism, in which the intermediate zwitterions 11a and 11b equilibrate (Scheme 6). In contrast, cis-1,2,3-triphenylaziridine (cis-1b) and 7a gave only one stereoisomeric pyrrolidine-3,4-dicarboxylate 10, with the configuration expected on the basis of orbital-symmetry control, i.e., via concerted reaction steps (Scheme 10). The configuration of 8a and 10, as well as that of a derivative of 8b, were established by X-ray crystallography.

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Aziridines-IV Catalytic decomposition of phenyldiazomethane in Schiff's bases

Cited by 44 publications

References 15 publications

Concerted vs. Non‐Concerted 1,3‐Dipolar Cycloadditions of Azomethine Ylides to Electron‐Deficient Dialkyl 2,3‐Dicyanobut‐2‐enedioates

Concerted vs. Non‐Concerted 1,3‐Dipolar Cycloadditions of Azomethine Ylides to Electron‐Deficient Dialkyl 2,3‐Dicyanobut‐2‐enedioates

1,3-Dipolar Cycloaddition Reactions of Azomethine Ylides with Carbonyl Dipolarophiles Yielding Oxazolidine Derivatives

Thermal [2+3]‐Cycloadditions of trans‐1‐Methyl‐2,3‐diphenylaziridine with CS and CC Dipolarophiles: An Unexpected Course with Dimethyl Dicyanofumarate

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