Regiospecific cycloaddition reaction of 2-aryl and 2-alkyl 1-arenesulfonylaziridines with isocyanates using sodium iodide

Nadir, U. K.; Basu, Nupur

doi:10.1016/s0040-4039(00)74786-1

Cited by 24 publications

(9 citation statements)

References 6 publications

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“…At 100 °C, the coupling proceeded smoothly and afforded 3 distinct heterocyclic products, a seven-membered product (2a), an oxazolidinone 3a, 7 and a trace amount of imidazolidinone 4a 7 (equation 1). (2) A variety of vinyl azirdines were evaluated in the thermal coupling reaction (equation 2, Table 1). 8 Electronic factors did not have much of an effect on the reaction as both para methoxy and para CF 3 substituted substrates afforded relatively equal ratios of heterocyclic products 2 and 3 (entries 2 and 3).…”

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“…However, the seven membered ring product (2b) was only observed in the reaction of the trans vinyl aziridine. We have recently found that the combination of Ni(COD) 2 and NHC ligands catalyze the reaction of vinyl aziridines and alkynes. 10 We surmised that this catalyst combination may facilitate the coupling of a wider range of vinyl aziridines and isocyanates and in a selective manner.…”

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“…As such, a series of NHCs were evaluated as potential ligands (Figure 1) for the Ni (0) catalyzed cycloaddition of isocyanates and vinylaziridines. Phenyl isocyanate (0.3M) 11 and N-benzyl-2-styryl-aziridine (1a, 0.1M) were again chosen as model substrates in a reaction catalyzed by 5 mol% Ni(COD) 2 and 10 mol% NHC in toluene at 100 °C (equation 5). Again, 3 heterocyclic products were generally observed.…”

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confidence: 99%

“…To address these possibilities, 1a and PhNCO were heated to 100 °C until a mixture of 2a and 3a were obtained. Two equivalents of 1b and catalytic amounts of Ni(COD) 2 and IMes were then added to the solution and the reaction was further heated to 100 °C. Interestingly, 4a trans was the only observed product (Scheme 1).…”

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Coupling of vinyl aziridines and phenyl isocyanate

Zhang

Chopade

Louie

2008

Tetrahedron Letters

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Thermal coupling of vinyl aziridines and phenyl isocyanate was evaluated. Although oxazolidinone products were predominant, some reactions afforded a seven-membered ring heterocycle. When Ni/ IMes was employed as a catalyst, a wider array of vinyl aziridines underwent coupling reactions. The Ni catalyzed reactions generally afforded vinyl imidazolidinones as major products.Keywords phenyl isocyanate; vinyl aziridine; N-heterocyclic carbene; nickel; imidazolidinone; oxazolidinone; tetrahydro- [1,3]diazepin-2-oneThe coupling of an isocyanate and a vinylaziridine is an effective way to access heterocyclic ring systems. Although one example of a thermal coupling has been reported, 1 these reactions are typically catalyzed by Lewis acids such as sodium iodide 2 and nickel iodide. 3 These couplings generally afford vinyl-substituted five membered imidazolidinone products. Palladium catalysts have also been used to catalyze this coupling reaction and in some cases, these couplings display high enantioselectivity. 4,5,6 In each of these cycloadditions, the vinyl group acts to enhance the reactivity of the aziridine. For example, in non-metal mediated reactions the vinyl group is an activating group. In Pd catalyzed coupling reactions, the vinyl group enhances binding of the aziridine substrate. However, in all of these cases, incorporation of the vinyl group in the heterocycle is not observed.We present here a study detailing both thermal reactions and nickel catalyzed reactions of phenyl isocyanate and vinyl aziridines. These reactions afford interesting heterocyclic products in addition to the expected vinyl substituted imidazolidinone. Publisher's Disclaimer: This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final citable form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. NIH Public Access Author ManuscriptTetrahedron Lett. Author manuscript; available in PMC 2009 January 1. Published in final edited form as:Tetrahedron Lett. 2008 ; 49(27): 4306-4309. NIH-PA Author ManuscriptNIH-PA Author Manuscript NIH-PA Author ManuscriptDespite the lack of information regarding simple thermal coupling of isocyanates and vinyl aziridines, we found that N-benzyl-2-styryl-aziridine (1a) reacted readily with 3 equiv of phenyl isocyanate at elevated temperatures (equation 1). At 100 °C, the coupling proceeded smoothly and afforded 3 distinct heterocyclic products, a seven-membered product (2a), an oxazolidinone 3a, 7 and a trace amount of imidazolidinone 4a 7 (equation 1).(2)A variety of vinyl azirdines were evaluated in the thermal coupling reaction (equation 2, Table 1). 8 Electronic factors did not have much of an effect on the reaction as both para methoxy and para CF 3 s...

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Coupling of vinyl aziridines and phenyl isocyanate

Zhang

Chopade

Louie

2008

Tetrahedron Letters

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“…[18] Our unique zinc-mediated conditions enabled the (3 + 2) cycloadditions of N –sulfonyl aziridines with dialkyl- and disilyl-carbodiimides, unlike any previously published systems, [6,9] furnishing diisopropyliminoimidazolidine 9a and secondary imidazolidine 9b . In accordance with our observations in the isothiocyanate (3 + 2) cycloadditions, a variety of 2-arylaziridines were suitable reaction partners with diphenylcarbodiimide ( 9c–9e ).…”

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Stereoselective Lewis Acid Mediated (3+2) Cycloadditions of N‐H‐ and N‐Sulfonylaziridines with Heterocumulenes

Craig

O’Connor

Goldberg

et al. 2014

Chemistry A European J

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Alkyl and aryl isothiocyanates and carbodiimides are effective substrates in (3 + 2) cycloadditions with N–sulfonyl-2-substituted aziridines and 2-phenylaziridine for the synthesis of iminothiazolidines and iminoimidazolidines. Additionally, the stereoselective (3 + 2) cycloaddition of N–H- and N–sulfonylaziridines with isothiocyanates can be accomplished, allowing for the synthesis of highly enantioenriched iminothiazolidines. Evidence for an intimate ion-pair mechanism is presented herein in the context of these chemo-, regio-, and diastereoselective transformations.The demonstrated ability to remove the sulfonyl group from the heterocyclic products displays the utility of these compounds for further derivatization and application.

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Some Synthetic Uses of Double‐Bonded Functional Groups

Hoyle

2009

Patai's Chemistry of Functional Groups

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Regiospecific cycloaddition reaction of 2-aryl and 2-alkyl 1-arenesulfonylaziridines with isocyanates using sodium iodide

Cited by 24 publications

References 6 publications

Coupling of vinyl aziridines and phenyl isocyanate

Coupling of vinyl aziridines and phenyl isocyanate

Stereoselective Lewis Acid Mediated (3+2) Cycloadditions of N‐H‐ and N‐Sulfonylaziridines with Heterocumulenes

Some Synthetic Uses of Double‐Bonded Functional Groups

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