Aziridines. XXI. 1,4-Diazabicyclo[4.1.0]hept-4-enes and 1,1a-dihydro-1,2-diarylazirino[1,2-a]quinoxalines

Heine, Harold W.; Henzel, Richard P.

doi:10.1021/jo00838a037

Cited by 52 publications

(22 citation statements)

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“…Azomethine ylides have also been generated from aziridines fused to a quinoxoline ring system. The thermolytic ring-opening of 1,1a-dihydro-1,2-diarylazirino[1,2-a]quinoxalines 36 gave the intermediate azomethine ylides 37, which underwent cycloadditions with benzaldehyde (2a) and 4-nitrobenzaldehyde (2i) to give oxazolo[3,2-a]quinoxaline derivatives 38 (Scheme 7, Table 4) [38,60]. Scheme 7.…”

Section: Entry R 1 Product 20 (% Yieldmentioning

confidence: 99%

“…The most frequent type of 1,3-dipolar cycloaddition reaction of azomethine ylides is that with alkenyl or alkynyl dipolarophiles substituted with electron-withdrawing groups, providing access to pyrrolidine-containing molecules of biological [18,[22][23][24][25][26] or materials science interest [27][28][29][30][31]. The reactions with multiple bonded heteroatom systems such as carbonyl, thiocarbonyl, isothiocyanato, imino, isocyanato, nitrile, nitroso, and azo derivatives are also known, but less well studied [7,16,[32][33][34][35][36][37][38]. Less recognized is the ability of azomethine ylides to react with aromatic dipolarophiles when the aromatic system is embedded within a polycyclic aromatic hydrocarbon, tethered with the azomethine ylide (an intramolecular process) or substituted with highly electron withdrawing nitro groups [39].…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Entry R 1 Product 20 (% Yieldmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

Meyer

Ryan

2016

Molecules

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“…[I 1). Although [2 -1-31 cycloaddition of bicyclic aziridines to the carbony1 group of p-nitrobenzaldehyde has been reported (7) and addition of activated aromatic aldehydes to 3-aroylaziridines gives4-aroyloxazolidines 3 in good yield (8) (eq. [2]), more direct evidence for the intermediacy of the oxazolidiile species 1 was lacking.…”

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confidence: 99%

Thermal [2 + 3] cycloaddition of N-trichloroacetyldiphenylcyclopropenimine to 3-aroylaziridines and 3-carbomethoxyaziridines

Lown¹,

Westwood²,

Moser³

1970

Can. J. Chem.

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N-Trichloroacetyldiphenylcyclopropenimine reacted with either cis-or trarzs-3-benzoyl-1-cyclohexyl-2-m-nitrophenylaziridine in a [2+ 31 cycloaddition to the C=N bond of the imine to form (a) 5-benzoyl-2-m-nitrophenyl-4-(spirodiphenylcyclopropene)-3-(trichloroacetylhydrate)-imidazolidine and (b) l-cyclohexyl-4-(cis-1,2-diphenylvinyl)-3-dichloroacetyl-2-n-nitrophenylimidazoline. Similar reactions with other 3-aroylaziridines gave analogous irnidazolidines and imidazolines. Isolation of an unhydrated imidazolidine of type (a) in the corresponding addition with 3-carbomethoxy-1-cyclohexyl-2-phenylaziridine gave direct spectroscopic proof for the cyclopropene moiety in these adducts. The orientation of the 1,3 dipolar additions was confirmed by a reaction using a specifically 3-deuterated aziridine.The isolation of these adducts of type (a) strongly supports the previously suggested intermediacy of an oxazolidine in the analogous addition of 3-aroylaziridines to diphenylcyclopropenone.

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“…47, 4335 (1969) Many substituted aziridines will undergo thermal cleavage ofthe 2-3 bond to an azometliine ylid intermediate, and subsequent [2 + 31 cycloaddition can take place to the acetylenic bond and to activated alkenes, in many and stereospecifically (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14).…”

mentioning

confidence: 99%

Thermal [2 + 3] cycloaddition of imino compounds to 3-aroylaziridines. Synthesis of imidazolidines

Lown¹,

Moser²,

Westwood³

1969

Can. J. Chem.

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3-Aroylaziridines react with a variety of i~nines and aryl-N-sulfonylimines in ~.efluxing benzene to give imidazolidines in excellent yield. T h e orientation of the [2 + 31 cycloaddition of the intermediate azoniethine ylids to the C=;;N double bond was proven by synthesis of specifically 5-deuterated inlidazolidines. The reactions provide a convenient new general synthesis of imidazolidines.Canadian Journal of Chemistry. 47, 4335 (1969) Many substituted aziridines will undergo thermal cleavage ofthe 2-3 bond to an azometliine ylid intermediate, and subsequent [2 + 31 cycloaddition can take place to the acetylenic bond and to activated alkenes, in many and stereospecifically (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14).W e have reported the analogous thermally induced additions of 3-aroylaziridines to the polarized carbonyl bond of diphenylcyclopropenone with the formation of 4-aroyl-4-oxazolines (15) and to the C=S double bond of aryl isothiocyanates t o form 4-aroyl-5-arylimino-4-thiazolines (16). In a continuing study of these additions to heteromultiple bonds, we report the [2 + 31 cycloaddition of 3-aroylaziridines to activated imino con~pounds which provides a new synthesis of imidazolidines.Treatment of 3-benzoyl-1-isopropyl-2-phenylaziridine with an equimolar quantity of benzalaniline in refl~~xing toluene for 16 h, followed by chromatographic separation on alumina aKorded the imidazolidine 1 as a white crystalline solid in 24 "/,yield, m.p. 182". The nuclear magnetic resonance (11.m.r.) spectrum of 1 shows the isopropyl methyl groups are non-equivalent, indicating proxinlity to an asymmetric center in accordance with the proposed structure. While the initial product consisted of an isomeric mixture corresponding to cis and trans arrangement of protons at the 4 and 5 positions as shown by the 1l.m.r. spectrum, only the isomer described above could be obtained in solid form. This was assigned the cis geometry at the 4,5 positions on the basis of an 8 Hz c o~~p l i n g constant for the AB P~+ N /~H H I COAr R

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Aziridines. XXI. 1,4-Diazabicyclo[4.1.0]hept-4-enes and 1,1a-dihydro-1,2-diarylazirino[1,2-a]quinoxalines

Cited by 52 publications

References 0 publications

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

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

Thermal [2 + 3] cycloaddition of N-trichloroacetyldiphenylcyclopropenimine to 3-aroylaziridines and 3-carbomethoxyaziridines

Thermal [2 + 3] cycloaddition of imino compounds to 3-aroylaziridines. Synthesis of imidazolidines

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