Reaction of oxaziridine with heterocumulene. A ketene, isocyanates, and carbodiimide

Komatsu, Mitsuo; Ohshiro, Yoshiki; Hotta, Hiroshi; Sato, Masaaki; Agawa, Toshio

doi:10.1021/jo00921a020

Cited by 45 publications

(16 citation statements)

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“…In the first possible mechanism (Path A), insertion of the aryne into the C-O bond of the oxaziridine ring occurs by a concerted mechanism. Agawa28 and Troisi4 have suggested a similar cycloaddition mechanism for the formation of diarylisoxazolidine derivatives from oxaziridines. Another possible mechanism involves initial formation of a nitrone at the higher temperatures employed.…”

Section: Mechanism For Formation Of the Dihydrobenzisoxazolesmentioning

confidence: 95%

Synthesis of Dihydrobenzisoxazoles by the [3 + 2] Cycloaddition of Arynes and Oxaziridines

Kıvrak

Larock

2010

J. Org. Chem.

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Dihydrobenzisoxazoles are readily prepared in good yields by the [3+2] cycloaddition of oxaziridines and arynes. The reaction involves an unusual cleavage of the C-O bond of the oxaziridine and tolerates a variety of substituents on the oxaziridine and the o-(trimethylsilyl)aryl triflate to form aryl-, heteroaryl-, alkyl-and naphthyl-substituted dihydrobenzisoxazoles. The resulting halogen-substituted dihydrobenzisoxazoles are readily elaborated to more complex products using palladium-catalyzed crossing-coupling processes.

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Section: Mechanism For Formation Of the Dihydrobenzisoxazolesmentioning

confidence: 95%

Synthesis of Dihydrobenzisoxazoles by the [3 + 2] Cycloaddition of Arynes and Oxaziridines

Kıvrak

Larock

2010

J. Org. Chem.

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“…All the reactions were carried out under a nitrogen stream in the apparatus reported previously. 1 Materials, Phenyl isothiocyanate was purchased from a commercial source.…”

Section: Methodsmentioning

confidence: 99%

“…The reaction of 2-tert-butyloxaziridine If with phenyl isothiocyanate to yield the oxadiazolidinethione 12 can be rationalized by invoking the steric arguments used to explain the reaction of If with isocyanates and a carbodiimide. 1 The formation of the minor product 13 is ascribed to the replacement of a sulfur atom by an oxygen atom of an oxaziridine during the reaction, as the ir spectrum of the reaction mixture showed the formation of 13, and partly to the replacement during column chromatography.…”

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confidence: 99%

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Reaction of oxaziridine with sulfur-containing heterocumulenes

Komatsu¹,

Ohshiro²,

Yasuda³

et al. 1974

J. Org. Chem.

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The reactions of oxaziridines 1 with carbon disulfide (2) and phenyl isothiocyanate (8) have been studied. With carbon disulfide, 2-n-alkyl-or see-alkyloxaziridines give alkyl isothiocyanates (quantitatively), carbonyl compounds, and sulfur. Similar reactions between 1 and 8 form carbodiimides 9, but under mild experimental conditions 1 and 8 react to yield considerable amounts of either and/or the thiadiazolidinethione isomers 10 and 11. 2-tert-Butyloxaziridine If does not react with 2, but reacts with 8 to afford oxadiazolidinethione 12 and oxadiazolidinone 13.In the preceding paper,l we reported the reactions of oxaziridines with a ketene, isocyanates, and a carbodiimide, showing that the results are quite different from those of oxiranes and of aziridines. In the reactions, oxaziridines gave 1: 1 cycloadducts or unstable three-membered intermediates, which further reacted with the cumillenes to give stable heterocycles, with the release of carbonyl compounds.In the present study, the reactions with sulfur-containing heterocumulenes such as carbon disulfide and an isothiocyanate are described. From one heterocumulene, in these reactions, another heterocumulene was obtained along with a carbonyl compound and sulfur uia unstable intermediates. The further reactions of the intermediates giving heterocycles were also observed.Such a characteristic difference caused by a sulfur atom, which is generally a good leaving group or easily exchangeable with an oxygen atom, can be expected from the following reactions of the cumulenes. In the reactions with ethylene oxide, for example, carbon disulfide gives ethylene carbonate and ethylene trithiocarbonate2S3 and phenyl isothiocyanate gives 1,3-oxazolidin-%one4 9 5 or isocyanate t~i m e r ,~,~ though 1:l cycloadditions are observed in the reactions of propylene oxide,3 ethylene ~u l f i d e ,~ or aziridines7v8 with carbon disulfide, aziridines with phenyl isothiocyanate,8 and ethylene oxide with N-acyl isothiocyanate .5 Results and DiscussionReaction with Carbon Disulfide. In the reaction of 2-n-alkyl-or 2-cycloalkyloxaziridine la,c,e,g,j with carbon disulfide (Z), an isothiocyanate 3 was quantitatively obtained. The results are shown in Table I.The products were characterized by the strong infrared absorption band at 2120 cm-1 (N=C=S). They were identified and determined by glpc or by converting them into thiourea derivatives. No reaction was observed for 2-tert-butyloxaziridine If in refluxing carbon disulfide; and the rearrangement of the oxaziridine If to a-phenyl-Ntert-butylnitrone ( 5 ) occurred under severe conditions, but a small quantity of tert-butyl isothiocyanate was detected by ir and glpc. The reaction is assumed to proceed via a thiaziridinethione intermediate 6 (Scheme I), which readily decomposes into an isothiocyanate 3 and sulfur. A similar assumption has been proposed for the reactions of the oxaziridines with diphenylketene and with diphenylcarbodiimide. The decomposition of the intermediate 6 occurs much faster than its further reaction with carbon d...

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“…L'examen de la littérature [6e8] nous a permis de constater que la méthode mise au point par Beckmann est la plus utilisée pour accéder aux oxadiazolidin-5-ones. La deuxième méthode de synthèse de ces composés, signalée dans la littérature, est celle d'Agawa et al, [9] utilisant les oxaziridines comme précurseurs. O Découvert en 1957 par R. Graf [10], l'isocyanate de chlorosulfonyle 2 (CSI) est un hétérocumulène doué d'une réactivité exceptionnelle.…”

Section: Introductionunclassified

Réaction des N-oxydes de 2-hydroxybenzylidènealkylamines avec l'isocyanate de chlorosulfonyle : synthèse de nouveaux composés hétérocycliques

Kraı̈em

Kacem

Bahy

et al. 2007

Comptes Rendus. Chimie

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Reaction of oxaziridine with heterocumulene. A ketene, isocyanates, and carbodiimide

Cited by 45 publications

References 16 publications

Synthesis of Dihydrobenzisoxazoles by the [3 + 2] Cycloaddition of Arynes and Oxaziridines

Synthesis of Dihydrobenzisoxazoles by the [3 + 2] Cycloaddition of Arynes and Oxaziridines

Reaction of oxaziridine with sulfur-containing heterocumulenes

Réaction des N-oxydes de 2-hydroxybenzylidènealkylamines avec l'isocyanate de chlorosulfonyle : synthèse de nouveaux composés hétérocycliques

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